POSS Literature References

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The following list collects key literature on polyhedral oligomeric silsesquioxanes, beginning with the early studies of crystalline organosilsesquioxanes. The references are grouped into five topics that correspond to the sections of the POSS Article Index, and within each topic they are listed in chronological order. An overview of the cage, ladder, and open cage architectures to which these references relate is given in the post on the structures of oligomeric silsesquioxanes.

Fundamentals, Nomenclature and Cage Structure

An introduction to cage, ladder, and open cage architectures is given in the post on the structures of oligomeric silsesquioxanes, and the T8 and M/D/T/Q notation is explained in the post on silsesquioxane nomenclature.

(1) Barry, A. J.; Daudt, W. H.; Domicone, J. J.; Gilkey, J. W. Crystalline Organosilsesquioxanes *. J. Am. Chem. Soc. 1955, 77, 4248–4252.

(2) Frye, C. L.; Klosowski, J. M. So-Called “Ladder Structure” of Equilibrated Phenylsilsesquioxane. J. Am. Chem. Soc. 1971, 93, 4599–4601.

(3) Voronkov, M. G.; Lavrent’yev, V. I. Polyhedral Oligosilsesquioxanes and Their Homo Derivatives. In Inorganic Ring Systems; Boschke, F. L., Dewar, M. J. S., Dunitz, J. D., Hafner, K., Heilbronner, E., Itô, S., Lehn, J.-M., Niedenzu, K., Raymond, K. N., Rees, C. W., Schäfer, K., Vögtle, F., Wittig, G., Series Eds.; Springer Berlin Heidelberg: Berlin, Heidelberg, 1982; Vol. 102, pp 199–236.

(4) Feher, F. J.; Newman, D. A.; Walzer, J. F. Silsesquioxanes as Models for Silica Surfaces. J. Am. Chem. Soc. 1989, 111, 1741–1748.

(5) Baney, R. H.; Itoh, Maki.; Sakakibara, Akihito.; Suzuki, Toshio. Silsesquioxanes. Chem. Rev. 1995, 95, 1409–1430.

(6) Bolln, C.; Tsuchida, A.; Frey, H.; Mülhaupt, R. Thermal Properties of the Homologous Series of 8-Fold Alkyl-Substituted Octasilsesquioxanes. Chem. Mater. 1997, 9, 1475–1479.

(7) Xiang, K.-H.; Pandey, R.; Pernisz, U. C.; Freeman, C. Theoretical Study of Structural and Electronic Properties of H-Silsesquioxanes. J. Phys. Chem. B 1998, 102, 8704–8711.

(8) Li, G.; Wang, L.; Ni, H.; Pittman, C. U. Polyhedral Oligomeric Silsesquioxane (POSS) Polymers and Copolymers: A Review. Journal of Inorganic and Organometallic Polymers 2001, 11, 123–154.

(9) Dijkstra, T. W.; Duchateau, R.; van Santen, R. A.; Meetsma, A.; Yap, G. P. A. Silsesquioxane Models for Geminal Silica Surface Silanol Sites. A Spectroscopic Investigation of Different Types of Silanols. J. Am. Chem. Soc. 2002, 124, 9856–9864.

(10) Franco, R.; Kandalam, A. K.; Pandey, R.; Pernisz, U. C. Theoretical Study of Structural and Electronic Properties of Methyl Silsesquioxanes. J. Phys. Chem. B 2002, 106, 1709–1713.

(11) Tejerina, B.; Gordon, M. S. Insertion Mechanism of N2 and O 2 into T n ( n = 8, 10, 12)-Silsesquioxane Framework. J. Phys. Chem. B 2002, 106, 11764–11770.

(12) Kudo, T.; Machida, K.; Gordon, M. S. Exploring the Mechanism for the Synthesis of Silsesquioxanes. 4. The Synthesis of T 8. J. Phys. Chem. A 2005, 109, 5424–5429.

(13) Laine, R. M. Nanobuilding Blocks Based on the [OSiO1.5]x (x = 6, 8, 10) Octasilsesquioxanes. J. Mater. Chem. 2005, 15, 3725–3744.

(14) Shen, J.; Cheng, W.-D.; Wu, D.-S.; Li, X.-D.; Lan, Y.-Z.; Zhang, H.; Gong, Y.-J.; Li, F.-F.; Huang, S.-P. Modeling of Configurations and Third-Order Nonlinear Optical Properties of Methyl Silsesquioxanes. The Journal of Chemical Physics 2005, 122, 204709.

(15) Fina, A.; Tabuani, D.; Carniato, F.; Frache, A.; Boccaleri, E.; Camino, G. Polyhedral Oligomeric Silsesquioxanes (POSS) Thermal Degradation. Thermochimica Acta 2006, 440, 36–42.

(16) Lee, D. W.; Kawakami, Y. Incompletely Condensed Silsesquioxanes: Formation and Reactivity. Polym J 2007, 39, 230–238.

(17) Lickiss, P. D.; Rataboul, F. Chapter 1 - Fully Condensed Polyhedral Oligosilsesquioxanes (POSS): From Synthesis to Application. In Advances in Organometallic Chemistry; Fink, A. F. H. and M. J., Ed.; Academic Press, 2008; Vol. 57, pp 1–116.

(18) Park, E. S.; Ro, H. W.; Nguyen, C. V.; Jaffe, R. L.; Yoon, D. Y. Infrared Spectroscopy Study of Microstructures of Poly(Silsesquioxane)s. Chem. Mater. 2008, 20, 1548–1554.

(19) Zhen, C.-G.; Becker, U.; Kieffer, J. Tuning Electronic Properties of Functionalized Polyhedral Oligomeric Silsesquioxanes: A DFT and TDDFT Study. J. Phys. Chem. A 2009, 113, 9707–9714.

(20) Cordes, D. B.; Lickiss, P. D.; Rataboul, F. Recent Developments in the Chemistry of Cubic Polyhedral Oligosilsesquioxanes. Chem. Rev. 2010, 110, 2081–2173.

(21) Quadrelli, E. A.; Basset, J.-M. On Silsesquioxanes’ Accuracy as Molecular Models for Silica-Grafted Complexes in Heterogeneous Catalysis. Coord. Chem. Rev. 2010, 254, 707–728.

(22) Applications of Polyhedral Oligomeric Silsesquioxanes; Hartmann-Thompson, C., Ed.; Advances in Silicon Science; Springer Netherlands: Dordrecht, 2011; Vol. 3.

(23) Laine, R. M.; Roll, M. F. Polyhedral Phenylsilsesquioxanes. Macromolecules 2011, 44, 1073–1109.

(24) Blanco, I.; Abate, L.; Bottino, F. A.; Bottino, P.; Chiacchio, M. A. Thermal Degradation of Differently Substituted Cyclopentyl Polyhedral Oligomeric Silsesquioxane (CP-POSS) Nanoparticles. J Therm Anal Calorim 2012, 107, 1083–1091.

(25) Fouquet, T.; Phan, T. N. T.; Charles, L. Tandem Mass Spectrometry of Electrosprayed Polyhedral Oligomeric Silsesquioxane Compounds with Different Substituents. Rapid Commun. Mass Spectrom. 2012, 26, 765–774.

(26) Neyertz, S.; Brachet, P.; Brown, D.; Männle, F. The Structure of Amino-Functionalized Polyhedral Oligomeric Silsesquioxanes (POSS) Studied by Molecular Dynamics Simulations. Computational Materials Science 2012, 62, 258–265.

(27) Skelton, A. A.; Fried, J. R. The Insertion of Gas Molecules into Polyhedral Oligomeric Silsesquioxane (POSS) Cages: Understanding the Energy of Insertion Using Quantum Chemical Calculations. Physical Chemistry Chemical Physics 2013, 15, 4341.

(28) Endo, H.; Takeda, N.; Takanashi, M.; Imai, T.; Unno, M. Refractive Indices of Silsesquioxanes with Various Structures. Silicon 2015, 7, 127–132.

(29) Neyertz, S.; Brown, D.; Pilz, M.; Rival, N.; Arstad, B.; Männle, F.; Simon, C. The Stability of Amino-Functionalized Polyhedral Oligomeric Silsesquioxanes in Water. J. Phys. Chem. B 2015, 119, 6433–6447.

(30) Tshishimbi Muya, J.; Ceulemans, A.; Gopakumar, G.; Parish, C. A. Jahn–Teller Distortion in Polyoligomeric Silsesquioxane (POSS) Cations. J. Phys. Chem. A 2015, 119, 4237–4243.

(31) Xia, Y.; Yao, H.; Cui, M.; Ma, Y.; Kong, Z.; Wu, B.; Qi, Z.; Sun, Y. Theoretical and Experimental Investigations on Mono-Substituted and Multi-Substituted Functional Polyhedral Oligomeric Silsesquioxanes. RSC Adv. 2015, 5, 80339–80345.

(32) Blanco, I.; Bottino, F. A.; Abate, L. Influence of N-Alkyl Substituents on the Thermal Behaviour of Polyhedral Oligomeric Silsesquioxanes (POSSs) with Different Cage’s Periphery. Thermochimica Acta 2016, 623, 50–57.

(33) Croissant, J. G.; Cattoën, X.; Durand, J.-O.; Man, M. W. C.; Khashab, N. M. Organosilica Hybrid Nanomaterials with a High Organic Content: Syntheses and Applications of Silsesquioxanes. Nanoscale 2016, 8, 19945–19972.

(34) Organofunctional Silsesquioxanes http://web.archive.org/web/20160423025340/http://innosil.pl/en/organofunctional-silsesquioxanes (accessed Apr 8, 2017).

(35) Dudziec, B.; Marciniec, B. Double-Decker Silsesquioxanes: Current Chemistry and Applications. Curr. Org. Chem. 2017, 21, 2794–2813.

(36) Nowacka, M.; Fischer, C.; Kowalewska, A.; Hebda, M.; Hodor, K. Thermally Induced Phenomena Leading to Degradation of Poly(Silsesquioxane) Materials. European Polymer Journal 2017, 86, 17–28.

(37) Ghani, K.; Keshavarz, M. H.; Jafari, M.; Khademian, F. A Novel Method for Predicting Decomposition Onset Temperature of Cubic Polyhedral Oligomeric Silsesquioxane Derivatives. J Therm Anal Calorim 2018, 132, 761–770.

(38) Kaneko, Y. Ionic Silsesquioxanes: Preparation, Structure Control, Characterization, and Applications. Polymer 2018, 144, 205–224.

(39) 刘昊东朱光明; LIU Hao-dong, Z. G. Research progress in preparation of functionalized polyhedral oligomeric silsesquioxanes. 材料工程 2019, 47, 33–42.

(40) Du, Y.; Liu, H. Cage-like Silsesquioxanes-Based Hybrid Materials. Dalton Trans. 2020.

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Synthesis and Functionalization

The main preparative routes are discussed in the guide to the synthesis of POSS and in the post on the hydrolytic condensation route to octameric POSS.

(41) Olsson, K. Improved Preparation of Octakis(Alkylsilsesquioxanes). Arkiv foer Kemi 1958, 13, 367–378.

(42) Brown, J. F.; Vogt, L. H.; Prescott, P. I. Preparation and Characterization of the Lower Equilibrated Phenylsilsesquioxanes. J. Am. Chem. Soc. 1964, 86, 1120–1125.

(43) Frye, C. L.; Collins, W. T. Oligomeric Silsesquioxanes, (HSiO3/2)n. J. Am. Chem. Soc. 1970, 92, 5586–5588.

(44) Voronkov, M. G.; Martynova, T. N.; Mirskov, R. G.; Belyi, V. I. Octavinylsilsesquioxane. Russian Journal of Organic Chemistry 1979, 49, 1522–1525.

(45) Feher, F. J.; Budzichowski, T. A. Syntheses of Highly-Functionalized Polyhedral Oligosilsesquioxanes. Journal of Organometallic Chemistry 1989, 379, 33–40.

(46) Kovrigin, V. M.; Lavrent’ev, V. I. Chromatographic-Mass-Spectroscopic Study of the Mechanism of Fomation of Pervinyloctasilsesquioxane in Polycondensation of Vinyltrichlorosilane in Butanol. Russian Journal of Organic Chemistry 1989, 59, 377–383.

(47) Laine, R. M.; Rahn, J. A.; Youngdahl, K. A.; Babonneau, F.; Hoppe, M. L.; Zhang, Z. F.; Harrod, J. F. Synthesis and High Temperature Chemistry of Methylsilsesquioxane Polymers Produced by Titanium-Catalyzed Redistribution of Methylhydridooligo- and -Polysiloxanes. Chem. Mater. 1990, 2, 464–472.

(48) Feher, F. J.; Budzichowski, T. A.; Blanski, R. L.; Weller, K. J.; Ziller, J. W. Facile Syntheses of New Incompletely Condensed Polyhedral Oligosilsesquioxanes: [(C-C5H9)7Si7O9(OH)3], [(c-C7H13)7Si7O9(OH)3], and [(c-C7H13)6Si6O7(OH)4]. Organometallics 1991, 10, 2526–2528.

(49) Weidner, R.; Zeller, N.; Deubzer, B.; Frey, V. Organooligosilsesquioxanes. 5047492, 1991.

(50) Dittmar, U.; Hendan, B. J.; Fl, U. Funktionalisierte Octa-(propylsilsesquioxane) (3-XC 3H 6) 8(SisO 12) Modellverbindungen fiir oberfl ichenmodifizierte Kieselgele. Journal of Organometallic Chemistry 1995, 10.

(51) Feher, F. J.; Weller, K. J.; Schwab, J. J. Reactions of Hydrosilsesquioxanes and Chlorosilsesquioxanes with Phosphoranes. Organometallics 1995, 14, 2009–2017.

(52) Unno, M.; Alias, S. B.; Saito, H.; Matsumoto, H. Synthesis of Hexasilsesquioxanes Bearing Bulky Substituents: Hexakis((1,1,2-Trimethylpropyl)Silsesquioxane) and Hexakis( Tert -Butylsilsesquioxane). Organometallics 1996, 15, 2413–2414.

(53) Zhang, C.; Laine, R. M. Silsesquioxanes as Synthetic Platforms. II. Epoxy-Functionalized Inorganic-Organic Hybrid Species. Journal of Organometallic Chemistry 1996, 521, 199–201.

(54) Feher, F. J.; Phillips, S. H.; Ziller, J. W. Facile and Remarkably Selective Substitution Reactions Involving Framework Silicon Atoms in Silsesquioxane Frameworks. J. Am. Chem. Soc. 1997, 119, 3397–3398.

(55) Feher, F. J.; Soulivong, D.; Lewis, G. T. Facile Framework Cleavage Reactions of a Completely Condensed Silsesquioxane Framework. J. Am. Chem. Soc. 1997, 119, 11323–11324.

(56) Harrison, P. G.; Hall, C. PREPARATION AND CHARACTERIZATION OF OCTASILSESQUIOXANE CAGE MONOMERS : Main Group Metal Chemistry. 1997, 20, 515–529.

(57) Rikowski, E.; Marsmann, H. C. Cage-Rearrangement of Silsesquioxanes. Polyhedron 1997, 16, 3357–3361.

(58) Feher, F. J.; Wyndham, K. D. Amine and Ester-Substituted Silsesquioxanes: Synthesis, Characterization and Use as a Core for Starburst Dendrimers. Chem. Commun. 1998, No. 3, 323–324.

(59) Feher, F. Practical Methods for Synthesizing Four Incompletely Condensed Silsesquioxanes from a Single R 8 Si 8 O 12 Framework. Chemical Communications 1998, No. 12, 1279–1280.

(60) Feher, F.; Wyndham, K.; Scialdone, M. Octafunctionalized Polyhedral Oligosilsesquioxanes as Scaffolds: Synthesis of Peptidyl Silsesquioxanes. Chemical Communications 1998, No. 14, 1469–1470.

(61) Jaffrès, P.-A.; Morris, R. E. Synthesis of Highly Functionalised Dendrimers Based on Polyhedral Silsesquioxane Cores. Journal of the Chemical Society, Dalton Transactions 1998, 16, 2767–2770.

(62) Feher, F. J.; Terroba, R.; Ziller, J. W. Base-Catalyzed Cleavage and Homologation of Polyhedral Oligosilsesquioxanes. Chemical Communications 1999, No. 21, 2153–2154.

(63) Feher, F. J.; Wyndham, K. D.; Soulivong, D.; Nguyen, F. Syntheses of Highly Functionalized Cube-Octameric Polyhedral Oligosilsesquioxanes (R8Si8O12). J. Chem. Soc., Dalton Trans. 1999, No. 9, 1491–1498.

(64) Gravel, M.-C.; Zhang, C.; Dinderman, M.; Laine, R. M. Octa(3-Chloroammoniumpropyl) Octasilsesquioxane. Appl. Organometal. Chem. 1999, 13, 329–336.

(65) Lücke, S.; Stoppek-Langner, K.; Kuchinke, J.; Krebs, B. Octakis-(Dimethylphosphanoethyl)-Octasilsesquioxane–Synthesis, Characterization and Reactivity. Journal of Organometallic Chemistry 1999, 584, 11–15.

(66) Eisenberg, P.; Erra-Balsells, R.; Ishikawa, Y.; Lucas, J. C.; Mauri, A. N.; Nonami, H.; Riccardi, C. C.; Williams, R. J. J. Cagelike Precursors of High-Molar-Mass Silsesquioxanes Formed by the Hydrolytic Condensation of Trialkoxysilanes. Macromolecules 2000, 33, 1940–1947.

(67) Unno, M.; Suto, A.; Takada, K.; Matsumoto, H. Synthesis of Ladder and Cage Silsesquioxanes from 1,2,3,4-Tetrahydroxycyclotetrasiloxane. BCSJ 2000, 73, 215–220.

(68) Zhang, C.; Laine, R. M. Hydrosilylation of Allyl Alcohol with [HSiMe2OSiO1.5]8: Octa(3-Hydroxypropyldimethylsiloxy)Octasilsesquioxane and Its Octamethacrylate Derivative as Potential Precursors to Hybrid Nanocomposites. J. Am. Chem. Soc. 2000, 122, 6979–6988.

(69) Manson, B. W.; Morrison, J. J.; Coupar, P. I.; Jaffrès, P.-A.; Morris, R. E. Synthesis of Aldehyde Functionalised Polyhedral Oligomeric Silsesquioxanes. J. Chem. Soc., Dalton Trans. 2001, No. 7, 1123–1127.

(70) Tamaki, R.; Tanaka, Y.; Asuncion, M. Z.; Choi, J.; Laine, R. M. Octa(Aminophenyl)Silsesquioxane as a Nanoconstruction Site. J. Am. Chem. Soc. 2001, 123, 12416–12417.

(71) Wada, K.; Izuhara, D.; Yamada, K.; Shiotsuki, M.; Kondo, T.; Mitsudo, T. Synthesis of Alkenylene-Bridged Macrocyclic Silsesquioxanes by Ruthenium or Rhodium-Catalyzed Ring-Closing Reactions of Bis(Allyldimethylsilyl) Groups. Chemical Communications 2001, No. 18, 1802–1803.

(72) Neumann, D.; Fisher, M.; Tran, L.; Matisons, J. G. Synthesis and Characterization of an Isocyanate Functionalized Polyhedral Oligosilsesquioxane and the Subsequent Formation of an Organic−Inorganic Hybrid Polyurethane. J. Am. Chem. Soc. 2002, 124, 13998–13999.

(73) Bassindale, A. R.; Liu, Z.; MacKinnon, I. A.; Taylor, P. G.; Yang, Y.; Light, M. E.; Horton, P. N.; Hursthouse, M. B. A Higher Yielding Route for T8 Silsesquioxane Cages and X-Ray Crystal Structures of Some Novel Spherosilicates. Dalton Trans. 2003, No. 14, 2945–2949.

(74) Bassindale, A. R.; MacKinnon, I. A.; Maesano, M. G.; Taylor, P. G. The Preparation of Hexasilsesquioxane (T 6 ) Cages by “Non Aqueous” Hydrolysis of Trichlorosilanes. Chem. Commun. 2003, No. 12, 1382–1383.

(75) dell’ Erba, I. E.; Fasce, D. P.; Williams, R. J. J.; Erra-Balsells, R.; Fukuyama, Y.; Nonami, H. Poly(Silsesquioxanes) Derived from the Hydrolytic Condensation of Organotrialkoxysilanes Containing Hydroxyl Groups. Journal of Organometallic Chemistry 2003, 686, 42–51.

(76) König, H. J.; Marsmann, H. C.; Letzel, M. C. Thioether Functionalized Octasilsesquioxanes. In Organosilicon Chemistry V; Auner, N., Weis, J., Eds.; Wiley-VCH Verlag GmbH, 2003; pp 425–428.

(77) Unno, M.; Imai, Y.; Matsumoto, H. Hexakis(2,4,6-Triisopropylphenylsilsesquioxane). Silicon Chemistry 2003, 2, 175–178.

(78) Bassindale, A. R.; Chen, H.; Liu, Z.; MacKinnon, I. A.; Parker, D. J.; Taylor, P. G.; Yang, Y.; Light, M. E.; Horton, P. N.; Hursthouse, M. B. A Higher Yielding Route to Octasilsesquioxane Cages Using Tetrabutylammonium Fluoride, Part 2: Further Synthetic Advances, Mechanistic Investigations and X-Ray Crystal Structure Studies into the Factors That Determine Cage Geometry in the Solid State. Journal of Organometallic Chemistry 2004, 689, 3287–3300.

(79) Gao, Y.; Eguchi, A.; Kakehi, K.; Lee, Y. C. Efficient Preparation of Glycoclusters from Silsesquioxanes. Org. Lett. 2004, 6, 3457–3460.

(80) Brick, C. M.; Tamaki, R.; Kim, S.-G.; Asuncion, M. Z.; Roll, M.; Nemoto, T.; Ouchi, Y.; Chujo, Y.; Laine, R. M. Spherical, Polyfunctional Molecules Using Poly(Bromophenylsilsesquioxane)s as Nanoconstruction Sites. Macromolecules 2005, 38, 4655–4660.

(81) Gao, J.; Wang, S.; Zhang, X.; Run, M. Synthesis of Cage Octa(Vinyl)​Silsesquioxane. Youjigui Cailiao 2005, 19, 5–7.

(82) Gültek, A.; Seçkın, T.; Adigüzel, H. İ. Design and Characterization of Amino and Chloro Functionalized Rhombohedral Silsesquioxanes. Turkish Journal of Chemistry 2005, 29, 391–399.

(83) Pakjamsai, C.; Kawakami, Y. Study on Effective Synthesis and Properties of Ortho-Alkyl-Substituted Phenyl Octasilsesquioxane. Designed Monomers & Polymers 2005, 8, 423–435.

(84) Wada, K.; Watanabe, N.; Yamada, K.; Kondo, T.; Mitsudo, T. Synthesis of Novel Starburst and Dendritic Polyhedral Oligosilsesquioxanes. Chemical Communications 2005, No. 1, 95.

(85) Dare, E. O.; Liu, L.-K.; Peng, J. Modified Procedure for Improved Synthesis of Some Octameric Silsesquioxanes via Hydrolytic Polycondenzation in the Presence of Amberlite Ion-Exchange Resins. Dalton Trans. 2006, No. 30, 3668–3671.

(86) Iacono, S. T.; Vij, A.; Grabow, W.; Smith, Jr., D. W.; Mabry, J. M. Facile Synthesis of Hydrophobic Fluoroalkyl Functionalized Silsesquioxane Nanostructures. Chem. Commun. 2007, No. 47, 4992–4994.

(87) Kawakami, Y.; Yamaguchi, K.; Yokozawa, T.; Serizawa, T.; Hasegawa, M.; Kabe, Y. Higher Polyhedral Silsesquioxane (POSS) Cage by Amine-Catalyzed Condensation of Silanols and Related Siloxanes. Chemistry Letters 2007, 36, 792–793.

(88) Valencia, M.; Dempwolf, W.; Günzler, F.; Knöpfelmacher, O.; Schmidt-Naake, G. Synthesis and Characterization of Silsesquioxane Prepolymers Bearing Phenyl and Methacryloxypropyl Groups Obtained by Cohydrolysis. Macromolecules 2007, 40, 40–46.

(89) Zhang, Z.; Liang, G.; Lu, T. Synthesis and Characterization of Cage Octa(Aminopropylsilsesquioxane). J. Appl. Polym. Sci. 2007, 103, 2608–2614.

(90) Asuncion, M. Z.; Roll, M. F.; Laine, R. M. Octaalkynylsilsesquioxanes, Nano Sea Urchin Molecular Building Blocks for 3-D-Nanostructures. Macromolecules 2008, 41, 8047–8052.

(91) Cheng, G.; Vautravers, N. R.; Morris, R. E.; Cole-Hamilton, D. J. Synthesis of Functional Cubes from Octavinylsilsesquioxane (OVS). Org. Biomol. Chem. 2008, 6, 4662–4667.

(92) Koželj, M.; Orel, B. Synthesis of Polyhedral Phenylsilsesquioxanes with KF as the Source of the Fluoride Ion. Dalton Transactions 2008, No. 37, 5072.

(93) Mabry, J. M.; Vij, A.; Iacono, S. T.; Viers, B. D. Fluorinated Polyhedral Oligomeric Silsesquioxanes (F-POSS). Angew. Chem. Int. Ed. 2008, 47, 4137–4140.

(94) Marciniec, B.; Dutkiewicz, M.; Maciejewski, H.; Kubicki, M. New, Effective Method of Synthesis and Structural Characterization of Octakis(3-Chloropropyl)Octasilsesquioxane. Organometallics 2008, 27, 793–794.

(95) Roll, M. F.; Asuncion, M. Z.; Kampf, J.; Laine, R. M. Para-Octaiodophenylsilsesquioxane, [p-IC6H4SiO1.5]8, a Nearly Perfect Nano-Building Block. ACS Nano 2008, 2, 320–326.

(96) Ervithayasuporn, V.; Wang, X.; Kawakami, Y. Synthesis and Characterization of Highly Pure Azido-Functionalized Polyhedral Oligomeric Silsesquioxanes (POSS). Chem. Commun. 2009, No. 34, 5130–5132.

(97) Ren, Z.; Cao, X.; Xie, P.; Zhang, R.; Yan, S.; Ma, Y. Supramolecular Architecture-Directed Synthesis of a Reactive and Purely Inorganic Ladder Polyhydrosilsesquioxane. Chemical Communications 2009, No. 27, 4079.

(98) Asuncion, M. Z.; Laine, R. M. Fluoride Rearrangement Reactions of Polyphenyl- and Polyvinylsilsesquioxanes as a Facile Route to Mixed Functional Phenyl, Vinyl T10 and T12 Silsesquioxanes. J. Am. Chem. Soc. 2010, 132, 3723–3736.

(99) Asuncion, M. Z.; Ronchi, M.; Abu-Seir, H.; Laine, R. M. Synthesis, Functionalization and Properties of Incompletely Condensed “Half Cube” Silsesquioxanes as a Potential Route to Nanoscale Janus Particles. Comptes Rendus Chimie 2010, 13, 270–281.

(100) Fabritz, S.; Heyl, D.; Bagutski, V.; Empting, M.; Rikowski, E.; Frauendorf, H.; Balog, I.; Fessner, W.-D.; Schneider, Jörg. J.; Avrutina, O.; Kolmar, H. Towards Click Bioconjugations on Cube-Octameric Silsesquioxane Scaffolds. Organic & Biomolecular Chemistry 2010, 8, 2212.

(101) Kawakami, Y.; Kabe, Y. Novel Meta -Selective Friedel–Crafts Acylation of Phenylsilsesquioxane. Chem. Lett. 2010, 39, 1082–1083.

(102) Miyazato, A.; Pakjamsai, C.; Kawakami, Y. Octa, Deca, and Dodeca(4-Nitrophenyl) Cage Silsesquioxanes via 4-Trimethylsilylphenyl Derivatives. Dalton Trans. 2010, 39, 3239–3244.

(103) Roll, M. F.; Mathur, P.; Kampf, J. W.; Laine, R. M. HYBRID NANO-BUILDING BLOCKS VIA SELECTIVE BROMINATION OF OCTAPHENYLSILSESQUIOXANE. Polymer Preprints 2010, 51, 359–360.

(104) Ronchi, M.; Sulaiman, S.; Boston, N. R.; Laine, R. M. Fluoride Catalyzed Rearrangements of Polysilsesquioxanes, Mixed Me, Vinyl T8, Me, Vinyl T10 and T12 Cages. Appl. Organometal. Chem. 2010, 24, 551–557.

(105) Tateyama, S.; Kakihana, Y.; Kawakami, Y. Cage Octaphenylsilsesquioxane from Cyclic Tetrasiloxanetetraol and Its Sodium Salt. Journal of Organometallic Chemistry 2010, 695, 898–902.

(106) Trastoy, B.; Pérez-Ojeda, M. E.; Sastre, R.; Chiara, J. L. Octakis (3-Azidopropyl) Octasilsesquioxane: A Versatile Nanobuilding Block for the Efficient Preparation of Highly Functionalized Cube-Octameric Polyhedral Oligosilsesquioxane Frameworks Through Click Assembly. Chemistry-A European Journal 2010, 16, 3833–3841.

(107) Ervithayasuporn, V.; Tomeechai, T.; Takeda, N.; Unno, M.; Chaiyanurakkul, A.; Hamkool, R.; Osotchan, T. Synthesis and Characterization of Octakis(3-Propyl Ethanethioate)Octasilsesquioxane. Organometallics 2011, 30, 4475–4478.

(108) Liu, H.; Puchberger, M.; Schubert, U. A Facile Route to Difunctionalized Monosubstituted Octasilsesquioxanes. Chem. Eur. J. 2011, 17, 5019–5023.

(109) Ramirez, S. M.; Diaz, Y. J.; Campos, R.; Stone, R. L.; Haddad, T. S.; Mabry, J. M. Incompletely Condensed Fluoroalkyl Silsesquioxanes and Derivatives: Precursors for Low Surface Energy Materials. J. Am. Chem. Soc. 2011, 133, 20084–20087.

(110) Żak, P.; Marciniec, B.; Majchrzak, M.; Pietraszuk, C. Highly Effective Synthesis of Vinylfunctionalised Cubic Silsesquioxanes. Journal of Organometallic Chemistry 2011, 696, 887–891.

(111) Cai, H.; Xu, K.; Liu, X.; Fu, Z.; Chen, M. A Facile Synthesis of Octa(Carboxyphenyl)Silsesquioxane. Dalton Trans. 2012, 41, 6919–6921.

(112) Fabritz, S.; Hörner, S.; Könning, D.; Empting, M.; Reinwarth, M.; Dietz, C.; Glotzbach, B.; Frauendorf, H.; Kolmar, H.; Avrutina, O. From Pico to Nano: Biofunctionalization of Cube-Octameric Silsesquioxanes by Peptides and Miniproteins. Org. Biomol. Chem. 2012, 10, 6287.

(113) Jaroentomeechai, T.; Yingsukkamol, P.; Phurat, C.; Somsook, E.; Osotchan, T.; Ervithayasuporn, V. Synthesis and Reactivity of Nitrogen Nucleophiles-Induced Cage-Rearrangement Silsesquioxanes. Inorg. Chem. 2012, 51, 12266–12272.

(114) Kaneko, Y.; Shoiriki, M.; Mizumo, T. Preparation of Cage-like Octa(3-Aminopropyl)Silsesquioxane Trifluoromethanesulfonate in Higher Yield with a Shorter Reaction Time. J. Mater. Chem. 2012, 22, 14475–14478.

(115) Kaneko, Y.; Toyodome, H.; Shoiriki, M.; Iyi, N. Preparation of Ionic Silsesquioxanes with Regular Structures and Their Hybridization. International Journal of Polymer Science 2012, 2012, 1–14.

(116) Lee, A. S.; Choi, S.-S.; Lee, H. S.; Baek, K.-Y.; Hwang, S. S. A New, Higher Yielding Synthetic Route towards Dodecaphenyl Cage Silsesquioxanes: Synthesis and Mechanistic Insights. Dalton Trans. 2012, 41, 10585–10588.

(117) Yue, K.; Liu, C.; Guo, K.; Yu, X.; Huang, M.; Li, Y.; Wesdemiotis, C.; Cheng, S. Z. D.; Zhang, W.-B. Sequential “Click” Approach to Polyhedral Oligomeric Silsesquioxane-Based Shape Amphiphiles. Macromolecules 2012, 45, 8126–8134.

(118) Ervithayasuporn, V.; Pornsamutsin, N.; Prangyoo, P.; Sammawutthichai, K.; Jaroentomeechai, T.; Phurat, C.; Teerawatananond, T. One-Pot Synthesis of Halogen Exchanged Silsesquioxanes: Octakis(3-Bromopropyl)Octasilsesquioxane and Octakis(3-Iodopropyl)Octasilsesquioxane. Dalton Trans. 2013, 42, 13747–13753.

(119) Ervithayasuporn, V.; Chimjarn, S. Synthesis and Isolation of Methacrylate- and Acrylate-Functionalized Polyhedral Oligomeric Silsesquioxanes (T8, T10, and T12) and Characterization of the Relationship between Their Chemical Structures and Physical Properties. Inorg. Chem. 2013, 52, 13108–13112.

(120) Fabritz, S.; Hörner, S.; Avrutina, O.; Kolmar, H. Bioconjugation on Cube-Octameric Silsesquioxanes. Org. Biomol. Chem. 2013, 11, 2224–2236.

(121) Jung, J. H.; Chou, K.; Furgal, J. C.; Laine, R. M. Synthesis of Acetoxyphenyl- and Hydroxyphenyl-Terminated Polyfunctional T8, T10, T12 Silsesquioxanes and Initial Studies on Their Use in the Formation of Highly Crosslinked Polyesters. Appl. Organometal. Chem. 2013, 27, n/a-n/a.

(122) Koech, J. K.; Shao, Q.; Mutua, F. N.; Wang, Y. Application of Hydrazine Hydrate in the Synthesis of Octa(Aminophenyl)Silsesquioxane (OAPS) Poss. Advances in Chemical Engineering and Science 2013, 03, 93–97.

(123) Koželj, M.; Orel, B. N-Heterocyclic Carbenes – Catalysts for the Preparation of Polyhedral Silsesquioxanes. Dalton Transactions 2013, 42, 9432.

(124) Pérez-Ojeda, M. E.; Trastoy, B.; Rol, Á.; Chiara, M. D.; García-Moreno, I.; Chiara, J. L. Controlled Click-Assembly of Well-Defined Hetero-Bifunctional Cubic Silsesquioxanes and Their Application in Targeted Bioimaging. Chem. Eur. J. 2013, 19, 6630–6640.

(125) Pu, Y.-J.; Yuan, H.; Yang, M.; He, B.; Gu, Z.-W. Synthesis of Peptide Dendrimers with Polyhedral Oligomeric Silsesquioxane Cores via Click Chemistry. Chinese Chemical Letters 2013, 24, 917–920.

(126) Boday, D. J.; Tolbert, S.; Keller, M. W.; Li, Z.; Wertz, J. T.; Muriithi, B.; Loy, D. A. Non-Hydrolytic Formation of Silica and Polysilsesquioxane Particles from Alkoxysilane Monomers with Formic Acid in Toluene/Tetrahydrofuran Solutions. Journal of Nanoparticle Research 2014, 16.

(127) Endo, H.; Takeda, N.; Unno, M. Synthesis and Properties of Phenylsilsesquioxanes with Ladder and Double-Decker Structures. Organometallics 2014, 33, 4148–4151.

(128) Feng, X.; Zhu, S.; Yue, K.; Su, H.; Guo, K.; Wesdemiotis, C.; Zhang, W.-B.; Cheng, S. Z. D.; Li, Y. T10 Polyhedral Oligomeric Silsesquioxane-Based Shape Amphiphiles with Diverse Head Functionalities via “Click” Chemistry. ACS Macro Lett. 2014, 3, 900–905.

(129) Janeta, M.; John, Ł.; Ejfler, J.; Szafert, S. High-Yield Synthesis of Amido-Functionalized Polyoctahedral Oligomeric Silsesquioxanes by Using Acyl Chlorides. Chem. Eur. J. 2014, 20, 15966–15974.

(130) Li, Y.; Guo, K.; Su, H.; Li, X.; Feng, X.; Wang, Z.; Zhang, W.; Zhu, S.; Wesdemiotis, C.; Cheng, S. Z. D.; Zhang, W.-B. Tuning “Thiol-Ene” Reactions toward Controlled Symmetry Breaking in Polyhedral Oligomeric Silsesquioxanes. Chem. Sci. 2014, 5, 1046–1053.

(131) Peng, J.; Xu, K.; Cai, H.; Wu, J.; Lin, W.; Yu, Z.; Chen, M. Can an Intact and Crystalline Octakis(Methacryloxypropyl) Silsesquioxane Be Prepared by Hydrolysis-Condensation of a Trimethoxysilane Precursor? RSC Advances 2014, 4, 7124.

(132) Riaz, A. Functionalized Polyhedral Oligomeric Silsesquioxane (POSS) for Incorporation of Chemically Pendant Chains. 2014, 171.

(133) Shanmugan, S.; Cani, D.; Pescarmona, P. P. The Design and Synthesis of an Innovative Octacarboxy-Silsesquioxane Building Block. Chem. Commun. 2014, 50, 11008–11011.

(134) Wang, X.; Ye, Q.; Song, J.; Cho, C. M.; He, C.; Xu, J. Fluorinated Polyhedral Oligomeric Silsesquioxanes. RSC Adv. 2014, 5, 4547–4553.

(135) Chimjarn, S.; Kunthom, R.; Chancharone, P.; Sodkhomkhum, R.; Sangtrirutnugul, P.; Ervithayasuporn, V. Synthesis of Aromatic Functionalized Cage-Rearranged Silsesquioxanes (T 8 , T 10 , and T 12 ) via Nucleophilic Substitution Reactions. Dalton Trans. 2015, 44, 916–919.

(136) Dumitriu, A.-C.; Cazacu, M.; Bargan, A.; Balan, M.; Vornicu, N.; Varganici, C.-D.; Shova, S. Full Functionalized Silica Nanostructure with Well-Defined Size and Functionality: Octakis(3-Mercaptopropyl)Octasilsesquioxane. Journal of Organometallic Chemistry 2015, 799–800, 195–200.

(137) Janeta, M.; John, Ł.; Ejfler, J.; Szafert, S. Novel Organic–Inorganic Hybrids Based on T 8 and T 10 Silsesquioxanes: Synthesis, Cage-Rearrangement and Properties. RSC Adv. 2015, 5, 72340–72351.

(138) Ledin, P. A.; Xu, W.; Friscourt, F.; Boons, G.-J.; Tsukruk, V. V. Branched Polyhedral Oligomeric Silsesquioxane Nanoparticles Prepared via Strain-Promoted 1,3-Dipolar Cycloadditions. Langmuir 2015, 31, 8146–8155.

(139) Liu, L.; Lee, S. J.; Lee, M. E.; Kang, P.; Choi, M.-G. Syntheses of Phosphorylcholine-Substituted Silsesquioxanes via Thiol-Ene ‘Click’ Reaction. Tetrahedron Letters 2015, 56, 1562–1565.

(140) Marchesi, S.; Carniato, F.; Palin, L.; Boccaleri, E. POSS as Building-Blocks for the Preparation of Polysilsesquioxanes through an Innovative Synthetic Approach. Dalton Trans. 2015, 44, 2042–2046.

(141) Xue, L.; Li, L.; Feng, S.; Liu, H. A Facile Route to Multifunctional Cage Silsesquioxanes via the Photochemical Thiol–Ene Reaction. Journal of Organometallic Chemistry 2015, 783, 49–54.

(142) Basenko, S. V.; Maylyan, A. A. Hexa(Organylsilsesquioxanes). Russian Chemical Bulletin 2016, 65, 1034–1038.

(143) Blázquez-Moraleja, A.; Pérez-Ojeda, M. E.; Suárez, J. R.; Jimeno, M. L.; Chiara, J. L. Efficient Multi-Click Approach to Well-Defined Two-Faced Octasilsesquioxanes: The First Perfect Janus Nanocube. Chem. Commun. 2016, 52, 5792–5795.

(144) Franczyk, A.; Stefanowska, K.; Dutkiewicz, M.; Frąckowiak, D.; Marciniec, B. A Highly Selective Synthesis of New Alkenylsilsesquioxanes by Hydrosilylation of Alkynes. Dalton Trans. 2016, 46, 158–164.

(145) Hanprasit, S.; Tungkijanansin, N.; Prompawilai, A.; Eangpayung, S.; Ervithayasuporn, V. Synthesis and Isolation of Non-Chromophore Cage-Rearranged Silsesquioxanes from Base-Catalyzed Reactions. Dalton Trans. 2016, 45, 16117–16120.

(146) Imoto, H.; Wada, S.; Naka, K. Efficient Isolation of Completely Decorated Polyhedral Oligomeric Silsesquioxanes by Utilizing Imine Bond Formation. Chem. Lett. 2016, 45, 1256–1258.

(147) Li, L.; Liu, H. Rapid Preparation of Silsesquioxane-Based Ionic Liquids. Chemistry - A European Journal 2016, 22, 4713–4716.

(148) Oguri, N.; Egawa, Y.; Takeda, N.; Unno, M. Janus-Cube Octasilsesquioxane: Facile Synthesis and Structure Elucidation. Angew. Chem. Int. Ed. 2016, 55, 9336–9339.

(149) Rzonsowska, M.; Dudziec, B.; Marciniec, B. Synthesis of a New Class of Silsesquioxanes with Alkynyl and Germyl Functionality. Dalton Transactions 2016, 45, 17187–17194.

(150) Sodkhomkhum, R.; Ervithayasuporn, V. Synthesis of Poly(Siloxane/Double-Decker Silsesquioxane) via Dehydrocarbonative Condensation Reaction and Its Functionalization. Polymer 2016, 86, 113–119.

(151) Szafert, S.; Janeta, M. P.; John, Ł. Patent USA: Method of Converting Polyhedral Oligomeric Silsesquioxane (POSS) Type T8 into Type 10. 9365595, June 14, 2016.

(152) Żak, P.; Frąckowiak, D.; Grzelak, M.; Bołt, M.; Kubicki, M.; Marciniec, B. Olefin Metathesis of Vinylgermanium Derivatives as Method for the Synthesis of Functionalized Cubic and Double-Decker Germasilsesquioxanes. Advanced Synthesis & Catalysis 2016, 358, 3265–3276.

(153) Imai, K.; Kaneko, Y. Preparation of Ammonium-Functionalized Polyhedral Oligomeric Silsesquioxanes with High Proportions of Cagelike Decamer and Their Facile Separation. Inorg. Chem. 2017.

(154) Koizumi, R.; Kimura, T.; Nakabayashi, K.; Mori, H. Amphiphilic Silsesquioxane Nanoparticles by Hydrolytic Condensation of Y-Shaped Triethoxysilanes Having Hydroxyl and Fluoroalkyl Groups: Synthesis, Self-Assembly, and Surface Properties. Polymer 2017, 110, 260–272.

(155) Brząkalski, D.; Rzonsowska, M.; Dudziec, B. Regioselective Formation of β -( E )- and α -Alkenylsilane Moiety Attached to Silsesquioxane Core via Pt- and Ru-Based Hydrosilylation: New β-(E)- and α- Alkenyl-Siloxy-Silsesquioxanes. Applied Organometallic Chemistry 2018, 32, e4267.

(156) Czaban-Jóźwiak, J.; Woźniak, Ł.; Ulikowski, A.; Kwiecińska, K.; Rajkiewicz, A.; Grela, K. Modification of Polyhedral Oligomeric Silsesquioxanes (POSS) Molecules by Ruthenium Catalyzed Cross Metathesis. Molecules 2018, 23, 1722.

(157) Mituła, K.; Dudziec, B.; Marciniec, B. Synthesis of Dialkenyl-Substituted Double-Decker Silsesquioxanes as Precursors for Linear Copolymeric Systems. Journal of Inorganic and Organometallic Polymers and Materials 2018, 28, 500–507.

(158) Mituła, K.; Dutkiewicz, M.; Dudziec, B.; Marciniec, B.; Czaja, K. A Library of Monoalkenylsilsesquioxanes as Potential Comonomers for Synthesis of Hybrid Materials. Journal of Thermal Analysis and Calorimetry 2018, 132, 1545–1555.

(159) Żak, P.; Delaude, L.; Dudziec, B.; Marciniec, B. N-Heterocyclic Carbene-Based Ruthenium-Hydride Catalysts for the Synthesis of Unsymmetrically Functionalized Double-Decker Silsesquioxanes. Chemical Communications 2018, 54, 4306–4309.

(160) Tahir Gunkara, O. Modification of Polyhedral Oligomeric Silsesquioxane Derivatives with Heck Reaction as Possible New Bio-Hybrid Materials. Phosphorus, Sulfur, and Silicon and the Related Elements 2019, 1–8.

(161) Kaźmierczak, J.; Lewandowski, D.; Hreczycho, G. B(C 6 F 5 ) 3 -Catalyzed Dehydrocoupling of POSS Silanols with Hydrosilanes: A Metal-Free Strategy for Effecting Functionalization of Silsesquioxanes. Inorganic Chemistry 2020.

(162) Laird, M.; Van der Lee, A.; Dumitrescu, D. G.; Carcel, C.; Ouali, A.; Bartlett, J. R.; Unno, M.; Wong Chi Man, M. Styryl-Functionalized Cage Silsesquioxanes as Nanoblocks for 3-D Assembly. Organometallics 2020.

(163) Matsumoto, T.; Kaneko, Y. Correlation between Molecular Structures and Reaction Conditions (Temperature–Pressure–Time) in the Preparation of Secondary, Tertiary, and Quaternary Ammonium-Functionalized Polyhedral Oligomeric Silsesquioxanes. J Sol-Gel Sci Technol 2020.

(164) Imoto, H.; Ueda, Y.; Sato, Y.; Nakamura, M.; Mitamura, K.; Watase, S.; Naka, K. Corner- and Side-Opened Cage Silsesquioxanes: Structural Effects on the Materials Properties. European Journal of Inorganic Chemistry n/a.

(165) Kanfar, N.; Mehdi, A.; Dumy, P.; Ulrich, S.; Winum, J.-Y. Polyhedral Oligomeric Silsesquioxane (POSS) Bearing Glyoxylic Aldehyde as Clickable Platform Towards Multivalent Conjugates. Chem. Eur. J. n/a-n/a.

(166) Kaźmierczak, J.; Kuciński, K.; Stachowiak, H.; Hreczycho, G. Introduction of Boron Functionalities into Silsesquioxanes - Novel Independent Methodologies. Chem. Eur. J. n/a-n/a.

(167) Marciniec, B. Functionalization of Polyhedral Oligomeric Silsesquioxane (POSS) via  Nucleophilic Substitutio https://www.thieme-connect.de/products/ejournals/pdf/10.1055/s-0029-1216807.pdf (accessed Jun 2, 2016).

(168) Symmetric Functionalization of Polyhedral Phenylsilsesquioxanes as a Route to Nano-Building Blocks.

(169) Sulaiman, S. Synthesis and Characterization of Polyfunctional Polyhedral Silsesquioxane Cages. 198.

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Crystal Structures and Supramolecular Chemistry

Structurally characterized metal complexes of silsesquioxanes are reviewed in the post on crystallographically confirmed metal POSS complexes.

(170) Vogt, L. H.; Brown, J. F. Crystalline Methylsilsesquioxanes. Inorg. Chem. 1963, 2, 189–192.

(171) Feher, F. J.; Budzichowski, T. A.; Weller, K. J. Polyhedral Aluminosilsesquioxanes: Soluble Organic Analogs of Aluminosilicates. J. Am. Chem. Soc. 1989, 111, 7288–7289.

(172) Feher, F. J.; Walzer, J. F. Synthesis and Characterization of Vanadium-Containing Silsesquioxanes. Inorg. Chem. 1991, 30, 1689–1694.

(173) Feher, F. J.; Budzichowski, T. A.; Rahimian, K.; Ziller, J. W. Reactions of Incompletely-Condensed Silsesquioxanes with Pentamethylantimony: A New Synthesis of Metallasilsesquioxanes with Important Implications for the Chemistry of Silica Surfaces. J. Am. Chem. Soc. 1992, 114, 3859–3866.

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(176) Auner, N.; Ziemer, B.; Herrschaft, B.; Ziche, W.; John, P.; Weis, J. Structural Studies of Novel Siloxysilsesquioxanes. European Journal of Inorganic Chemistry 1999, 1999, 1087–1094.

(177) Duchateau, R.; Harmsen, R. J.; Abbenhuis, H. C. L.; van Santen, R. A.; Meetsma, A.; Thiele, S. K.-H.; Kranenburg, M. Modeling Acidic Sites in Zeolites and Aluminosilicates by Aluminosilsesquioxanes. Chem. Eur. J. 1999, 5, 3130–3135.

(178) Skowronska-Ptasinska, M. D.; Duchateau, R.; van Santen, R. A.; Yap, G. P. A. Methyl Aluminosilsesquioxanes, Models for Lewis Acidic Silica-Grafted Methyl Aluminum Species. Organometallics 2001, 20, 3519–3530.

(179) Deng, J.; Polidan, J. T.; Hottle, J. R.; Farmer-Creely, C. E.; Viers, B. D.; Esker, A. R. Polyhedral Oligomeric Silsesquioxanes:  A New Class of Amphiphiles at the Air/Water Interface. J. Am. Chem. Soc. 2002, 124, 15194–15195.

(180) Richter, I.; Burschka, C.; Tacke, R. Octakis[(2,2,6,6-Tetramethylpiperidino)Methyl]Octasilsesquioxane: Synthesis and Crystal Structure Analysis of a New Aminoorganyl-Functionalized Octasilsesquioxane. Journal of Organometallic Chemistry 2002, 646, 200–203.

(181) Bassindale, A. R.; Pourny, M.; Taylor, P. G.; Hursthouse, M. B.; Light, M. E. Fluoride-Ion Encapsulation within a Silsesquioxane Cage. Angew. Chem. Int. Ed. 2003, 42, 3488–3490.

(182) Gerritsen, G.; Duchateau, R.; Yap, G. P. A. Boron, Aluminum, and Gallium Silsesquioxane Compounds, Homogeneous Models for Group 13 Element-Containing Silicates and Zeolites. Organometallics 2003, 22, 100–110.

(183) Bassindale, A. R.; Parker, D. J.; Pourny, M.; Taylor, P. G.; Horton, P. N.; Hursthouse, M. B. Fluoride Ion Entrapment in Octasilsesquioxane Cages as Models for Ion Entrapment in Zeolites. Further Examples, X-Ray Crystal Structure Studies, and Investigations into How and Why They May Be Formed. Organometallics 2004, 23, 4400–4405.

(184) Hanssen, R. W. J. M.; van Santen, R. A.; Abbenhuis, H. C. L. The Dynamic Status Quo of Polyhedral Silsesquioxane Coordination Chemistry. Eur. J. Inorg. Chem. 2004, 2004, 675–683.

(185) Lorenz, V.; Gießmann, S.; Gun’ko, Y. K.; Fischer, A. K.; Gilje, J. W.; Edelmann, F. T. Fully Metalated Silsesquioxanes: Building Blocks for the Construction of Catalyst Models. Angew. Chem. Int. Ed. 2004, 43, 4603–4606.

(186) Riollet, V.; Quadrelli, E. A.; Copéret, C.; Basset, J.-M.; Andersen, R. A.; Köhler, K.; Böttcher, R.-M.; Herdtweck, E. Grafting of [Mn(CH2tBu)2(Tmeda)] on Silica and Comparison with Its Reaction with a Silsesquioxane. Chem. Eur. J. 2005, 11, 7358–7365.

(187) Cui, L.; Collet, J. P.; Xu, G.; Zhu, L. Supramolecular Self-Assembly in a Disk-Cube Dyad Molecule Based on Triphenylene and Polyhedral Oligomeric Silsesquioxane (POSS). Chem. Mater. 2006, 18, 3503–3512.

(188) Lucenti, E.; D’Alfonso, G.; Macchi, P.; Maranesi, M.; Roberto, D.; Sironi, A.; Ugo, R. A Re(CO)5 Fragment Bonded to a Polyhedral Oligomeric Hydroxysilsesquioxane as a Model Which Gives Further Evidence to the Existence of an Unexpected Re(CO)5 Surface Species. J. Am. Chem. Soc. 2006, 128, 12054–12055.

(189) Lucenti, E.; Feher, F. J.; Ziller, J. W. Synthesis and Characterization of Osmium-Containing Silsesquioxanes: High-Yield Routes to {Os 3 (CO) 10 (μ-H)[(μ-O)Si 7 O 10 ( c -C 6 H 11 ) 7 ]} and the New Clusters {Os 3 (CO) 10 (μ-H)[(μ-O)Si 7 O 9 (OH) 2 ( c -C 6 H 11 ) 7 ]}, {[Os 3 (CO) 10 (μ-H)] 2 (μ-O) 2 Si 7 O 9 (OH)( c -C 6 H 11 ) 7 }, {Os 3 (CO) 10 (μ-H)[(μ-O)Si 8 O 11 (OH)( c -C 6 H 11 ) 8 ]}, and {[Os 3 (CO) 10 (μ-H)] 2 (μ-O) 2 Si 8 O 11 ( c -C 6 H 11 ) 8 }. Organometallics 2007, 26, 75–82.

(190) Anderson, S. E.; Bodzin, D. J.; Haddad, T. S.; Boatz, J. A.; Mabry, J. M.; Mitchell, C.; Bowers, M. T. Structural Investigation of Encapsulated Fluoride in Polyhedral Oligomeric Silsesquioxane Cages Using Ion Mobility Mass Spectrometry and Molecular Mechanics.”. Chem. Mater. 2008, 20, 4299–4309.

(191) Goodgame, D. M. L.; Kealey, S.; Lickiss, P. D.; White, A. J. P. Transition Metal Complexes of Cubic (T8) Oligo-Silsesquioxanes. J. Mol. Struct. 2008, 890, 232–239.

(192) Kaneko, Y.; Iyi, N. Sol–Gel Synthesis of Ladder Polysilsesquioxanes Forming Chiral Conformations and Hexagonal Stacking Structures. Journal of Materials Chemistry 2009, 19, 7106.

(193) Kuo, S.-W.; Lee, H.-F.; Huang, W.-J.; Jeong, K.-U.; Chang, F.-C. Solid State and Solution Self-Assembly of Helical Polypeptides Tethered to Polyhedral Oligomeric Silsesquioxanes. Macromolecules 2009, 42, 1619–1626.

(194) Miao, J.; Zhu, L. Topology Controlled Supramolecular Self-Assembly of Octa Triphenylene-Substituted Polyhedral Oligomeric Silsesquioxane Hybrid Supermolecules. The Journal of Physical Chemistry B 2010, 114, 1879–1887.

(195) Ohde, C.; Limberg, C.; Stösser, R.; Demeshko, S. Oxovanadium(IV) Silsesquioxane Complexes. Inorg. Chem. 2010, 49, 2479–2485.

(196) Yu, X.; Zhong, S.; Li, X.; Tu, Y.; Yang, S.; Van Horn, R. M.; Ni, C.; Pochan, D. J.; Quirk, R. P.; Wesdemiotis, C.; Zhang, W.-B.; Cheng, S. Z. D. A Giant Surfactant of Polystyrene−(Carboxylic Acid-Functionalized Polyhedral Oligomeric Silsesquioxane) Amphiphile with Highly Stretched Polystyrene Tails in Micellar Assemblies. J. Am. Chem. Soc. 2010, 132, 16741–16744.

(197) Zakharov, A. V.; Masters, S. L.; Wann, D. A.; Shlykov, S. A.; Girichev, G. V.; Arrowsmith, S.; Cordes, D. B.; Lickiss, P. D.; White, A. J. P. The Gas-Phase Structure of Octaphenyloctasilsesquioxane Si8O12Ph8 and the Crystal Structures of Si8O12(p-Tolyl)8 and Si8O12(p-ClCH2C6H4)8. Dalton Trans. 2010, 39, 6960.

(198) Daga, V. K.; Anderson, E. R.; Gido, S. P.; Watkins, J. J. Hydrogen Bond Assisted Assembly of Well-Ordered Polyhedral Oligomeric Silsesquioxane–Block Copolymer Composites. Macromolecules 2011, 44, 6793–6799.

(199) Kaneko, Y.; Toyodome, H.; Sato, H. Preparation of Chiral Ladder-like Polysilsesquioxanes and Their Chiral Induction to Anionic Dye Compound. Journal of Materials Chemistry 2011, 21, 16638.

(200) Li, Y.; Zhang, W.-B.; Hsieh, I.-F.; Zhang, G.; Cao, Y.; Li, X.; Wesdemiotis, C.; Lotz, B.; Xiong, H.; Cheng, S. Z. D. Breaking Symmetry toward Nonspherical Janus Particles Based on Polyhedral Oligomeric Silsesquioxanes: Molecular Design, “Click” Synthesis, and Hierarchical Structure. J. Am. Chem. Soc. 2011, 133, 10712–10715.

(201) Roll, M. F.; Kampf, J. W.; Laine, R. M. Crystalline Hybrid Polyphenylene Macromolecules from Octaalkynylsilsesquioxanes, Crystal Structures, and a Potential Route to 3-D Graphenes. Macromolecules 2011, 44, 3425–3435.

(202) Roll, M. F.; Kampf, J. W.; Laine, R. M. Halogen Bonding Motifs in Polyhedral Phenylsilsesquioxanes: Effects of Systematic Variations in Geometry or Substitution. Crystal Growth & Design 2011, 11, 4360–4367.

(203) Seki, H.; Abe, N.; Abe, Y.; Gunji, T. Synthesis and Structure of Syn , Anti , Syn -Pentacyclic Ladder Oligomethylsilsesquioxane. Chemistry Letters 2011, 40, 722–723.

(204) Tanabe, M.; Mutou, K.; Mintcheva, N.; Osakada, K. Preparation and Reactivity of an O,O-Chelating Silsesquioxane–Palladium Complex. Journal of Organometallic Chemistry 2011, 696, 1211–1215.

(205) Wang, X.; Ervithayasuporn, V.; Zhang, Y.; Kawakami, Y. Reversible Self-Assembly of Dendrimer Based on Polyhedral Oligomeric Silsesquioxanes (POSS). Chem. Commun. 2011, 47, 1282–1284.

(206) Taylor, P. G.; Bassindale, A. R.; El Aziz, Y.; Pourny, M.; Stevenson, R.; Hursthouse, M. B.; Coles, S. J. Further Studies of Fluoride Ion Entrapment in Octasilsesquioxane Cages; X-Ray Crystal Structure Studies and Factors That Affect Their Formation. Dalton Trans. 2012, 41, 2048–2059.

(207) El Aziz, Y.; Bassindale, A. R.; Taylor, P. G.; Stephenson, R. A.; Hursthouse, M. B.; Harrington, R. W.; Clegg, W. X-Ray Crystal Structures, Packing Behavior, and Thermal Stability Studies of a Homologous Series of n-Alkyl-Substituted Polyhedral Oligomeric Silsesquioxanes. Macromolecules 2013, 46, 988–1001.

(208) Liu, H.; Zhu, Q.; Feng, L.; Yao, B.; Feng, S. Synthesis, Structural Characterization and Properties of a Cubic Octa-n-Propylsilsesquioxane Inorganic–Organic Hybrid Material. Journal of Molecular Structure 2013, 1032, 29–34.

(209) Wang, Z.; Li, Y.; Dong, X.-H.; Yu, X.; Guo, K.; Su, H.; Yue, K.; Wesdemiotis, C.; Cheng, S. Z. D.; Zhang, W.-B. Giant Gemini Surfactants Based on Polystyrene–Hydrophilic Polyhedral Oligomeric Silsesquioxane Shape Amphiphiles: Sequential “Click” Chemistry and Solution Self-Assembly. Chem. Sci. 2013, 4, 1345–1352.

(210) Yuan, W.; Liu, X.; Zou, H.; Ren, J. Environment-Induced Nanostructural Dynamical-Change Based on Supramolecular Self-Assembly of Cyclodextrin and Star-Shaped Poly(Ethylene Oxide) with Polyhedral Oligomeric Silsesquioxane Core. Polymer 2013, 54, 5374–5381.

(211) Au-Yeung, H.-L.; Leung, S. Y.-L.; Tam, A. Y.-Y.; Yam, V. W.-W. Transformable Nanostructures of Platinum-Containing Organosilane Hybrids: Non-Covalent Self-Assembly of Polyhedral Oligomeric Silsesquioxanes Assisted by Pt···Pt and π–π Stacking Interactions of Alkynylplatinum(II) Terpyridine Moieties. J. Am. Chem. Soc. 2014, 136, 17910–17913.

(212) Chinnam, P. R.; Gau, M. R.; Schwab, J.; Zdilla, M. J.; Wunder, S. L. The Polyoctahedral Silsesquioxane (POSS) 1,3,5,7,9,11,13,15-Octaphenylpentacyclo[9.5.1.1 3,9 .1 5,15 .1 7,13 ]Octasiloxane (Octaphenyl-POSS). Acta Crystallographica Section C Structural Chemistry 2014, 70, 971–974.

(213) Khairova, R. R.; Yakimova, L. S.; Evtugyn, V. G.; Rizvanov, I. Kh.; Stoikov, I. I. The Synthesis of Phosphorylated Silsesquioxanes and the Investigation of the Ability to Aggregation and Interaction with Aromatic Dicarboxylic Acids. Journal of Organometallic Chemistry 2014, 772–773, 84–92.

(214) Wang, L.; Ishida, Y.; Maeda, R.; Tokita, M.; Horiuchi, S.; Hayakawa, T. Alkylated Cage Silsesquioxane Forming a Long-Range Straight Ordered Hierarchical Lamellar Nanostructure. Langmuir 2014, 30, 9797–9803.

(215) Zhang, W.; Hong, L.; McGowan, P. C. A Giant Capsule from the Self-Assembly of a Penta-Telechelic Hybrid Poly(Acrylic Acid) Based on Polyhedral Oligomeric Silsesquioxane. Macromolecular Chemistry and Physics 2014, 215, 900–905.

(216) Bilyachenko, A. N.; Dronova, M. S.; Yalymov, A. I.; Lamaty, F.; Bantreil, X.; Martinez, J.; Bizet, C.; Shul’pina, L. S.; Korlyukov, A. A.; Arkhipov, D. E.; Levitsky, M. M.; Shubina, E. S.; Kirillov, A. M.; Shul’pin, G. B. Cage-like Copper(II) Silsesquioxanes: Transmetalation Reactions and Structural, Quantum Chemical, and Catalytic Studies. Chem. Eur. J. 2015, 21, 8758–8770.

(217) Frąckowiak, D.; Żak, P.; Spólnik, G.; Pyziak, M.; Marciniec, B. New Vinylgermanium Derivatives of Silsesquioxanes and Their Ruthenium Complexes—Synthesis, Structure, and Reactivity. Organometallics 2015, 34, 3950–3958.

(218) Liu, F.; Zhang, Y.; Xu, L.; Zhang, W. Morphology-Controlled Self-Assembly of an Organic/Inorganic Hybrid Porphyrin Derivative Containing Polyhedral Oligomeric Silsesquioxane (POSS). Chem. Eur. J. 2015, 21, 5540–5547.

(219) Ma, C.; Wu, H.; Huang, Z.-H.; Guo, R.-H.; Hu, M.-B.; Kübel, C.; Yan, L.-T.; Wang, W. A Filled-Honeycomb-Structured Crystal Formed by Self-Assembly of a Janus Polyoxometalate–Silsesquioxane (POM–POSS) Co-Cluster. Angew. Chem. Int. Ed. 2015, 54, 15699–15704.

(220) Sanil, E. S.; Cho, K.-H.; Hong, D.-Y.; Lee, J. S.; Lee, S.-K.; Ryu, S. G.; Lee, H. W.; Chang, J.-S.; Hwang, Y. K. A Polyhedral Oligomeric Silsesquioxane Functionalized Copper Trimesate. Chem. Commun. 2015, 51, 8418–8420.

(221) Zhang, Y.; Zhang, L.; Liu, H.; Sun, D.; Li, X. Synthesis and Aggregation Properties of a Series of Dumbbell Polyhedral Oligosilsesquioxane-Perylene Diimide Triads. CrystEngComm 2015, 17, 1453–1463.

(222) Banerjee, S.; Kataoka, S.; Takahashi, T.; Kamimura, Y.; Suzuki, K.; Sato, K.; Endo, A. Controlled Formation of Ordered Coordination Polymeric Networks Using Silsesquioxane Building Blocks. Dalton Trans. 2016, 45, 17082–17086.

(223) Bilyachenko, A. N.; Yalymov, A. I.; Levitsky, M. M.; Korlyukov, A. A.; Es’kova, M. A.; Long, J.; Larionova, J.; Guari, Y.; Shul’pina, L. S.; Ikonnikov, N. S.; Trigub, A. L.; Zubavichus, Y. V.; Golub, I. E.; Shubina, E. S.; Shul’pin, G. B. First Cage-like Pentanuclear Co(II)-Silsesquioxane. Dalton Trans. 2016, 45, 13663–13666.

(224) Bilyachenko, A. N.; Yalymov, A. I.; Korlyukov, A. A.; Long, J.; Larionova, J.; Guari, Y.; Vologzhanina, A. V.; Es’kova, M. A.; Shubina, E. S.; Levitsky, M. M. Unusual Penta- and Hexanuclear Ni(II)-Based Silsesquioxane Polynuclear Complexes. Dalton Trans. 2016, 45, 7320–7327.

(225) Korlyukov, A. A.; Vologzhanina, A. V.; Buzin, M. I.; Sergienko, N. V.; Zavin, B. G.; Muzafarov, A. M. Cu(II)-Silsesquioxanes as Secondary Building Units for Construction of Coordination Polymers: A Case Study of Cesium-Containing Compounds. Crystal Growth & Design 2016.

(226) Kowalewska, A.; Nowacka, M.; Maniukiewicz, W. Octa(3-Mercaptopropyl)Octasilsesquioxane – A Reactive Nanocube of Unique Self-Assembled Packing Morphology. Journal of Organometallic Chemistry 2016, 810, 15–24.

(227) Au-Yeung, H.-L.; Tam, A. Y.-Y.; Leung, S. Y.-L.; Yam, V. W.-W. Supramolecular Assembly of Platinum-Containing Polyhedral Oligomeric Silsesquioxanes: An Interplay of Intermolecular Interactions and a Correlation between Structural Modifications and Morphological Transformations. Chem. Sci. 2017, 8, 2267–2276.

(228) Bilyachenko, A. N.; Kulakova, A. N.; Levitsky, M. M.; Petrov, A. A.; Korlyukov, A. A.; Shul’pina, L. S.; Khrustalev, V. N.; Dorovatovskii, P. V.; Vologzhanina, A. V.; Tsareva, U. S.; Golub, I. E.; Gulyaeva, E. S.; Shubina, E. S.; Shul’pin, G. B. Unusual Tri-, Hexa-, and Nonanuclear Cu(II) Cage Methylsilsesquioxanes: Synthesis, Structures, and Catalytic Activity in Oxidations with Peroxides. Inorg. Chem. 2017.

(229) Kowalewska, A.; Nowacka, M.; Włodarska, M.; Zgardzińska, B.; Zaleski, R.; Oszajca, M.; Krajenta, J.; Kaźmierski, S. Solid-State Dynamics and Single-Crystal to Single-Crystal Structural Transformations in Octakis(3-Chloropropyl)Octasilsesquioxane and Octavinyloctasilsesquioxane. Phys. Chem. Chem. Phys. 2017, 19, 27516–27529.

(230) Kowalewska, A. Self-Assembling Polyhedral Silsesquioxanes - Structure and Properties. Curr. Org. Chem. 2017, 21, 1243–1264.

(231) Raghuvanshi, A.; Strohmann, C.; Tissot, J.-B.; Clément, S.; Mehdi, A.; Richeter, S.; Viau, L.; Knorr, M. Assembly of Coordination Polymers Using Thioether‐Functionalized Octasilsesquioxanes: Occurrence of (CuX)n Clusters (X=Br and I) within 3D‐POSS Networks. Chemistry – A European Journal 2017, 23, 16479–16483.

(232) Voisin, D.; Flot, D.; Lee, A. V. der; Dautel, O. J.; Moreau, J. J. E. Hydrogen Bond-Directed Assembly of Silsesquioxanes Cubes: Synthesis of Carboxylic Acid POSS Derivatives and the Solid State Structure of Octa[2-(p-Carboxyphenyl)Ethyl] Silsesquioxane. CrystEngComm 2017, 19, 492–502.

(233) Zhang, M.-Y.; Zhou, S.; Pan, H.-B.; Ping, J.; Zhang, W.; Fan, X.-H.; Shen, Z. Structural Complexity Induced by Topology Change in Hybrids Consisting of Hexa-Peri-Hexabenzocoronene and Polyhedral Oligomeric Silsesquioxane. Chem. Commun. 2017.

(234) Huang, M.; Yue, K.; Huang, J.; Liu, C.; Zhou, Z.; Wang, J.; Wu, K.; Shan, W.; Shi, A.-C.; Cheng, S. Z. D. Highly Asymmetric Phase Behaviors of Polyhedral Oligomeric Silsesquioxane-Based Multiheaded Giant Surfactants. ACS Nano 2018, 12, 1868–1877.

(235) Li, S.; Wang, Z.-Y.; Gao, G.-G.; Li, B.; Luo, P.; Kong, Y.-J.; Liu, H.; Zang, S.-Q. Smart Transformation of a Polyhedral Oligomeric Silsesquioxane Shell Controlled by Thiolate Silver(I) Nanocluster Core in Cluster@Clusters Dendrimers. Angew. Chem. Int. Ed. 2018, 57, 12775–12779.

(236) Gomes, M. A. G. B.; Pessanha, Q. S. J.; Toledo, R.; Lube, L. M.; Fernandes, C.; Horn, A. Synthesis and Characterization of New Polyoctahedral Silsesquioxanes Containing Zinc Coordination Compounds on the Surface. Journal of Molecular Structure 2020, 1220, 128738.

(237) Piec, K.; Kostera, S.; Jędrzkiewicz, D.; Ejfler, J.; John, Ł. Mono-Substituted Amine-Oligosilsesquioxanes as Functional Tools in Pd(II) Coordination Chemistry: Synthesis and Properties. New J. Chem. 2020.

(238) Potsi, G.; Wu, J.; Portale, G.; Gengler, R. Y. N.; Longo, A.; Gournis, D.; Rudolf, P. Fabrication of Highly Ordered Cu2+/Fe3+ Decorated Polyhedral Oligomeric Silsesquioxane Hybrids: How Metal Coordination Influences Structure. Journal of Colloid and Interface Science 2020.

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Catalysis and Photochemistry

Catalytic applications are illustrated by the zinc imine POSS catalyst for CO2 cycloaddition and by POSS difluoroboron photocatalysts for sulfide oxidation.

(239) Feher, F. J. Polyhedral Oligometallasilsesquioxanes (POMSS) as Models for Silica-Supported Transition-Metal Catalysts.  Synthesis and Characterization of (C5Me5)Zr[(Si7O12)(c-C6H11)7]. J. Am. Chem. Soc. 1986, 108, 3850–3852.

(240) Feher, F. J.; Blanski, R. L. Olefin Polymerization by Vanadium-Containing Silsesquioxanes: Synthesis of a Dialkyl-Oxo-Vanadium(V) Complex That Initiates Ethylene Polymerization. J. Am. Chem. Soc. 1992, 114, 5886–5887.

(241) Feher, F. J.; Tajima, T. L. Synthesis of a Molybdenum-Containing Silsesquioxane Which Rapidly Catalyzes the Metathesis of Olefins. J. Am. Chem. Soc. 1994, 116, 2145–2146.

(242) Cauzzi, D.; Costa, M.; Gonsalvi, L.; Pellinghelli, M. A.; Predieri, G.; Tiripicchio, A.; Zanoni, R. Anchoring Rhodium(I) on Thiourea-Functionalized Silica Xerogels and Silsesquioxanes Part II. Matrix Effects on the Selectivity in the Hydroformylation of Styrene. Journal of Organometallic Chemistry 1997, 541, 377–389.

(243) Ossadnik, C.; Vepřek, S.; Marsmann, H. C.; Rikowski, E. Photolumineszenzeigenschaften von Substituierten Silsesquioxanen Der Zusammensetzung Rn (SiO1. 5) n. In Silicon Chemistry; Springer, 1999; pp 55–68.

(244) Nowotny, M.; Maschmeyer, T.; Johnson, B. F. G.; Lahuerta, P.; Thomas, J. M.; Davies, J. E. Heterogeneous Dinuclear Rhodium(II) Hydroformylation Catalysts—Performance Evaluation and Silsesquioxane-Based Chemical Modeling. Angew. Chem. Int. Ed. 2001, 40, 955–958.

(245) Duchateau, R. Incompletely Condensed Silsesquioxanes:  Versatile Tools in Developing Silica-Supported Olefin Polymerization Catalysts. Chem. Rev. 2002, 102, 3525–3542.

(246) Kapoor, M. P.; Sinha, A. K.; Seelan, S.; Inagaki, S.; Tsubota, S.; Yoshida, H.; Haruta, M. Hydrophobicity Induced Vapor-Phase Oxidation of Propene over Gold Supported on Titanium Incorporated Hybrid Mesoporous Silsesquioxane. Chem. Commun. 2002, No. 23, 2902–2903.

(247) Ropartz, L.; F. Foster, D.; E. Morris, R.; Z. Slawin, A. M.; J. Cole-Hamilton, D. Hydrocarbonylation Reactions Using Alkylphosphine-Containing Dendrimers Based on a Polyhedral Oligosilsesquioxane Core. Journal of the Chemical Society, Dalton Transactions 2002, 9, 1997–2008.

(248) Severn, J. R.; Duchateau, R.; Santen, R. A. van; Ellis, D. D.; Spek, A. L.; Yap, G. P. A. Silsesquioxane-Bonded Zirconocene Complexes; Soluble Models for Silica-Tethered Olefin Polymerization Catalysts. Dalton Trans. 2003, 2293–2302.

(249) Duchateau, R.; Dijkstra, T. W.; van Santen, R. A.; Yap, G. P. A. Silsesquioxane Models for Silica Surface Silanol Sites with Adjacent Siloxide Functionalites and Olefin Polymerization Catalysts Thereof. Chem. Eur. J. 2004, 10, 3979–3990.

(250) Pescarmona, P. P.; Masters, A. F.; van der Waal, J. C.; Maschmeyer, T. Osmium Silsesquioxane as Model Compound and Homogeneous Catalyst for the Dihydroxylation of Alkenes. J. Mol. Catal. Chem. 2004, 220, 37–42.

(251) Cho, H. M.; Weissman, H.; Wilson, S. R.; Moore, J. S. A Mo(VI) Alkylidyne Complex with Polyhedral Oligomeric Silsesquioxane Ligands:  Homogeneous Analogue of a Silica-Supported Alkyne Metathesis Catalyst. J. Am. Chem. Soc. 2006, 128, 14742–14743.

(252) Duchateau, R.; van Meerendonk, W. J.; Huijser, S.; Staal, B. B. P.; van Schilt, M. A.; Gerritsen, G.; Meetsma, A.; Koning, C. E.; Kemmere, M. F.; Keurentjes, J. T. F. Silica-Grafted Diethylzinc and a Silsesquioxane-Based Zinc Alkyl Complex as Catalysts for the Alternating Oxirane−Carbon Dioxide Copolymerization. Organometallics 2007, 26, 4204–4211.

(253) Jones, M. D.; Davidson, M. G.; Keir, C. G.; Wooles, A. J.; Mahon, M. F.; Apperley, D. C. Heterogeneous Catalysts for the Controlled Ring-Opening Polymerisation of Rac-Lactide and Homogeneous Silsesquioxane Model Complexes. Dalton Trans 2008, No. 28, 3655–3657.

(254) Sulaiman, S.; Bhaskar, A.; Zhang, J.; Guda, R.; Goodson, T.; Laine, R. M. Molecules with Perfect Cubic Symmetry as Nanobuilding Blocks for 3-D Assemblies. Elaboration of Octavinylsilsesquioxane. Unusual Luminescence Shifts May Indicate Extended Conjugation Involving the Silsesquioxane Core. Chem. Mater. 2008, 20, 5563–5573.

(255) Di Iulio, C.; Jones, M. D.; Mahon, M. F.; Apperley, D. C. Zinc(II) Silsesquioxane Complexes and Their Application for the Ring-Opening Polymerization of Rac-Lactide. Inorg. Chem. 2010, 49, 10232–10234.

(256) Laine, R. M.; Sulaiman, S.; Brick, C.; Roll, M.; Tamaki, R.; Asuncion, M. Z.; Neurock, M.; Filhol, J.-S.; Lee, C.-Y.; Zhang, J.; Goodson, T.; Ronchi, M.; Pizzotti, M.; Rand, S. C.; Li, Y. Synthesis and Photophysical Properties of Stilbeneoctasilsesquioxanes. Emission Behavior Coupled with Theoretical Modeling Studies Suggest a 3-D Excited State Involving the Silica Core. J. Am. Chem. Soc. 2010, 132, 3708–3722.

(257) Pérez-Ojeda, M. E.; Trastoy, B.; López-Arbeloa, Í.; Bañuelos, J.; Costela, Á.; García-Moreno, I.; Chiara, J. L. Click Assembly of Dye-Functionalized Octasilsesquioxanes for Highly Efficient and Photostable Photonic Systems. Chem. Eur. J. 2011, 17, 13258–13268.

(258) Zhou, J.; Zhao, Y.; Yu, K.; Zhou, X.; Xie, X. Synthesis, Thermal Stability and Photoresponsive Behaviors of Azobenzene-Tethered Polyhedral Oligomeric Silsesquioxanes. New J. Chem. 2011, 35, 2781–2792.

(259) Di Iulio, C.; Jones, M. D.; Mahon, M. F. Synthesis of Al(III) Silsesquioxane Complexes and Their Exploitation for the Ring Opening Polymerisation of Rac-Lactide. J. Organomet. Chem. 2012, 718, 96–100.

(260) Tang, S.; Jin, R.; Zhang, H.; Yao, H.; Zhuang, J.; Liu, G.; Li, H. Recoverable Organorhodium-Functionalized Polyhedral Oligomeric Silsesquioxane: A Bifunctional Heterogeneous Catalyst for Asymmetric Transfer Hydrogenation of Aromatic Ketones in Aqueous Medium. Chemical Communications 2012, 48, 6286.

(261) Ventura, M.; Mosquera, M. E. G.; Cuenca, T.; Royo, B.; Jiménez, G. Cyclopentadienyl–Silsesquioxane Titanium Complexes: Highly Active Catalysts for Epoxidation of Alkenes with Aqueous Hydrogen Peroxide. Inorg. Chem. 2012, 51, 6345–6349.

(262) Zheng, S.; Phillips, H.; Geva, E.; Dunietz, B. D. Ab Initio Study of the Emissive Charge-Transfer States of Solvated Chromophore-Functionalized Silsesquioxanes. J. Am. Chem. Soc. 2012, 134, 6944–6947.

(263) Ferrer-Ugalde, A.; Juárez-Pérez, E. J.; Teixidor, F.; Viñas, C.; Núñez, R. Synthesis, Characterization, and Thermal Behavior of Carboranyl-Styrene Decorated Octasilsesquioxanes: Influence of the Carborane Clusters on Photoluminescence. Chem. Eur. J. 2013, 19, 17021–17030.

(264) Furgal, J. C.; Jung, J. H.; Goodson, T.; Laine, R. M. Analyzing Structure–Photophysical Property Relationships for Isolated T8, T10, and T12 Stilbenevinylsilsesquioxanes. J. Am. Chem. Soc. 2013, 135, 12259–12269.

(265) Chen, X.; Zhang, P.; Wang, T.; Li, H. The First Europium(III) β-Diketonate Complex Functionalized Polyhedral Oligomeric Silsesquioxane. Chem. Eur. J. 2014, 20, 2551–2556.

(266) Leng, Y.; Liu, J.; Zhang, C.; Jiang, P. A Polyhedral Oligomeric Silsesquioxane (POSS)-Bridged Oxo-Molybdenum Schiff Base Complex with Enhanced Heterogeneous Catalytic Activity in Epoxidation. Catal. Sci. Technol. 2014, 4, 997–1004.

(267) Silva, P. S. da; Gasparini, B. C.; Magosso, H. A.; Spinelli, A. Gold Nanoparticles Hosted in a Water-Soluble Silsesquioxane Polymer Applied as a Catalytic Material onto an Electrochemical Sensor for Detection of Nitrophenol Isomers. Journal of Hazardous Materials 2014, 273, 70–77.

(268) Bivona, L. A.; Fichera, O.; Fusaro, L.; Giacalone, F.; Buaki-Sogo, M.; Gruttadauria, M.; Aprile, C. A Polyhedral Oligomeric Silsesquioxane-Based Catalyst for the Efficient Synthesis of Cyclic Carbonates. Catal. Sci. Technol. 2015, 5, 5000–5007.

(269) Ervithayasuporn, V.; Kwanplod, K.; Boonmak, J.; Youngme, S.; Sangtrirutnugul, P. Homogeneous and Heterogeneous Catalysts of Organopalladium Functionalized-Polyhedral Oligomeric Silsesquioxanes for Suzuki–Miyaura Reaction. J. Catal. 2015, 332, 62–69.

(270) Jefferson, L. U.; Netchaev, A. D.; Jefcoat, J. A.; Windham, A. D.; McFarland, F. M.; Guo, S.; Buchanan, R. K.; Buchanan, J. P. Preparation and Characterization of Polyhedral Oligomeric Silsesquioxane-Containing, Titania-Thiol-Ene Composite Photocatalytic Coatings, Emphasizing the Hydrophobic–Hydrophilic Transition. ACS Appl. Mater. Interfaces 2015, 7, 12639–12648.

(271) Leng, Y.; Zhao, J.; Jiang, P.; Wang, J. Amphiphilic Porous Polyhedral Oligomeric Silsesquioxanes (POSS) Incorporated Polyoxometalate-Paired Polymeric Hybrids: Interfacial Catalysts for Epoxidation Reactions. RSC Advances 2015, 5, 17709–17715.

(272) Liu, Y.; Yang, W.; Liu, H. Azobenzene-Functionalized Cage Silsesquioxanes as Inorganic-Organic Hybrid, Photoresponsive, Nanoscale, Building Blocks. Chemistry - A European Journal 2015, 21, 4731–4738.

(273) Yang, W.; Gan, Y.; Jiang, X.; Liu, H. Cinnamate-Functionalized Cage Silsesquioxanes as Photoreactive Nanobuilding Blocks. Eur. J. Inorg. Chem. 2015, 2015, 99–103.

(274) Yu, T.; Wang, X.; Su, W.; Zhang, C.; Zhao, Y.; Zhang, H.; Xu, Z. Synthesis and Photo- and Electro-Luminescent Properties of Ir(III) Complexes Attached to Polyhedral Oligomeric Silsesquioxane Materials. RSC Adv. 2015, 5, 80572–80582.

(275) Akbari, A.; Arsalani, N.; Amini, M.; Jabbari, E. Cube-Octameric Silsesquioxane-Mediated Cargo Copper Schiff Base for Efficient Click Reaction in Aqueous Media. Journal of Molecular Catalysis A: Chemical 2016, 414, 47–54.

(276) Li, W.; Yang, H.; Zhang, J.; Mu, J.; Gong, D.; Wang, X. Immobilization of Isolated FI Catalyst on Polyhedral Oligomeric Silsesquioxane-Functionalized Silica for the Synthesis of Weakly Entangled Polyethylene. Chem. Commun. 2016, 52, 11092–11095.

(277) Mohapatra, S.; Chaiprasert, T.; Sodkhomkhum, R.; Kunthom, R.; Hanprasit, S.; Sangtrirutnugul, P.; Ervithayasuporn, V. Solid-State Synthesis of Polyhedral Oligomeric Silsesquioxane-Supported N-Heterocyclic Carbenes/Imidazolium Salts on Palladium Nanoparticles: Highly Active and Recyclable Catalyst. ChemistrySelect 2016, 1, 5353–5357.

(278) Pochwała, M.; Białek, M.; Franczyk, A.; Marciniec, B.; Czaja, K. Synthesis and Catalytic Performance in Ethylene and 1-Octene Polymerization of Chlorotitanium(IV) Silsesquioxane Complexes. Effect of Increasing Ligand Denticity and Type of Nonreactive Organic Substituents. European Polymer Journal 2016, 79, 121–131.

(279) Sun, L.; Liu, Y.; Dang, S.; Wang, Z.; Liu, J.; Fu, J.; Shi, L. Lanthanide Complex-Functionalized Polyhedral Oligomeric Silsesquioxane with Multicolor Emission Covered from 450 Nm to 1700 Nm. New J. Chem. 2016, 40, 209–216.

(280) Zhou, H.; Li, J.; Chua, M. H.; Yan, H.; Ye, Q.; Song, J.; Lin, T. T.; Tang, B. Z.; Xu, J. Tetraphenylethene (TPE) Modified Polyhedral Oligomeric Silsesquioxanes (POSS): Unadulterated Monomer Emission, Aggregation-Induced Emission and Nanostructural Self-Assembly Modulated by the Flexible Spacer between POSS and TPE. Chem. Commun. 2016, 52, 12478–12481.

(281) Kunthom, R.; Jaroentomeechai, T.; Ervithayasuporn, V. Polyhedral Oligomeric Silsesquioxane (POSS) Containing Sulfonic Acid Groups as a Metal-Free Catalyst to Prepare Polycaprolactone. Polymer 2017, 108, 173–178.

(282) Sangtrirutnugul, P.; Chaiprasert, T.; Hunsiri, W.; Jitjaroendee, T.; Songkhum, P.; Laohhasurayotin, K.; Osotchan, T.; Ervithayasuporn, V. Tunable Porosity of Crosslinked-Polyhedral Oligomeric Silsesquioxane (POSS) Supports for Palladium-Catalyzed Aerobic Alcohol Oxidation in Water. ACS Appl. Mater. Interfaces 2017, 9, 12812–12822.

(283) Vieira, E. G.; Silva, R. O.; Junior, E. F.; Dias Filho, N. L. Synthesis, Characterization and Catalytic Application of a New Organometallic Oligomer Based on Polyhedral Oligomeric Silsesquioxane. Appl Organometal Chem 2017, n/a-n/a.

(284) Yu, T.; Niu, Y.; Yu, S.; Xu, Z.; Zhao, Y.; Zhang, H. Synthesis, Photo- and Electro-Luminescence of Novel Red Phosphorescent Ir(III) Complexes with a Silsesquioxane Core. Journal of Organometallic Chemistry 2017, 830, 85–92.

(285) Groch, P.; Dziubek, K.; Czaja, K.; Mituła, K.; Dudziec, B. Multi-Alkenylsilsesquioxanes as Comonomers and Active Species Modifiers of Metallocene Catalyst in Copolymerization with Ethylene. Polymers 2018, 10, 223.

(286) Luanphaisarnnont, T.; Hanprasit, S.; Somjit, V.; Ervithayasuporn, V. Chiral Pyrrolidine Bridged Polyhedral Oligomeric Silsesquioxanes as Heterogeneous Catalysts for Asymmetric Michael Additions. Catalysis Letters 2018, 148, 779–786.

(287) Sadjadi, S.; Malmir, M.; Heravi, M. M.; Raja, M. Magnetic Hybrid of Cyclodextrin Nanosponge and Polyhedral Oligomeric Silsesquioxane: Efficient Catalytic Support for Immobilization of Pd Nanoparticles. International Journal of Biological Macromolecules 2019, 128, 638–647.

(288) Janeta, M.; Lis, T.; Szafert, S. Zinc Imine Polyhedral Oligomeric Silsesquioxane as a Quattro-Site Catalyst for the Synthesis of Cyclic Carbonates from Epoxides and Low Pressure CO2. Chemistry – A European Journal 2020, n/a.

(289) Meng, X.; Liu, Y.; Wang, S.; Du, J.; Ye, Y.; Song, X.; Liang, Z. Silsesquioxane–Carbazole-Corbelled Hybrid Porous Polymers with Flexible Nanopores for Efficient CO2 Conversion and Luminescence Sensing. ACS Appl. Polym. Mater. 2020, 2, 189–197.

(290) Synthesis-and-Characterization-of-a-Polyhedral-Oligomeric-Silsesquioxane-Functionalized-Methyl-Re.Html.

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Materials, Sensing and Applications

Material applications are discussed in the posts on POSS polymer nanocomposites and on fluorescent silsesquioxane sensors.

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(393) Chawla, R.; Tan, A.; Ahmed, M.; Crowley, C.; Moiemen, N. S.; Cui, Z.; Butler, P. E.; Seifalian, A. M. A Polyhedral Oligomeric Silsesquioxane?Based Bilayered Dermal Scaffold Seeded with Adipose Tissue?Derived Stem Cells: In?Vitro Assessment of Biomechanical Properties. Journal of Surgical Research 2014, 188, 361–372.

(394) Chen, C.; Liang, X.; Wang, J.; Zou, Y.; Hu, H.; Cai, Q.; Yao, S. Development of a Polymeric Ionic Liquid Coating for Direct-Immersion Solid-Phase Microextraction Using Polyhedral Oligomeric Silsesquioxane as Cross-Linker. Journal of Chromatography A 2014, 1348, 80–86.

(395) Chen, S. C.; Fu, X. Z.; Chung, T.-S. Fouling Behaviors of Polybenzimidazole (PBI)?Polyhedral Oligomeric Silsesquioxane (POSS)/Polyacrylonitrile (PAN) Hollow Fiber Membranes for Engineering Osmosis Processes. Desalination 2014, 335, 17–26.

(396) Cui, H.-W.; Kuo, S.-W. Using Agrawal Integral Equation, Dynamic Mechanical Analysis (DMA), and Differential Scanning Calorimeter (DSC) Methods to Study the Glass Transition Kinetics of Nanocomposites of Polybenzoxazine and Exfoliated Montmorillonite from a Polyhedral Oligomeric Silsesquioxane Surfactant and Click Chemistry. Applied Clay Science 2014, 91–92, 1–5.

(397) Currivan, J. A.; Siddiqui, S.; Ahn, S.; Tryputen, L.; Beach, G. S. D.; Baldo, M. A.; Ross, C. A. Polymethyl Methacrylate/Hydrogen Silsesquioxane Bilayer Resist Electron Beam Lithography Process for Etching 25?Nm Wide Magnetic Wires. Journal of Vacuum Science & Technology B, Nanotechnology and Microelectronics: Materials, Processing, Measurement, and Phenomena 2014, 32, 021601.

(398) Devaraju, S.; Vengatesan, M. R.; Selvi, M.; Alagar, M. Thermal and Dielectric Properties of Newly Developed Linear Aliphatic-Ether Linked Bismaleimide-Polyhedral Oligomeric Silsesquioxane (POSS-AEBMI) Nanocomposites. Journal of Thermal Analysis and Calorimetry 2014, 117, 1047–1063.

(399) Do Carmo, D. R.; Silvestrini, D. R.; Barud, H. S.; Dias Filho, N. L.; Bicalho, U. O.; Soares, L. A. A Silsesquioxane Organically Modified with 4-Amino-5-(4-Pyridyl)-4 H -1,2,4-Triazole-3-Thiol: Thermal Behavior and Its Electrochemical Detection of Sulfhydryl Compounds. Journal of Nanomaterials 2014, 2014, 1–11.

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(401) Guan, C.; Yang, H.; Li, W.; Zhou, D.; Xu, J.; Chen, Z.-R. Crystallization Behavior of Ultrahigh-Molecular-Weight Polyethylene/Polyhedral Oligomeric Silsesquioxane Nanocomposites Prepared by Ethylene in Situ Polymerization: ARTICLE. Journal of Applied Polymer Science 2014, 131, n/a-n/a.

(402) He, H.-B.; Dong, C.; Li, B.; Dong, J.-P.; Bo, T.-Y.; Wang, T.-L.; Yu, Q.-W.; Feng, Y.-Q. Fabrication of Enrofloxacin Imprinted Organic–Inorganic Hybrid Mesoporous Sorbent from Nanomagnetic Polyhedral Oligomeric Silsesquioxanes for the Selective Extraction of Fluoroquinolones in Milk Samples. Journal of Chromatography A 2014, 1361, 23–33.

(403) Hong, L.; Zhang, Z.; Zhang, W. Synthesis of Organic/Inorganic Polyhedral Oligomeric Silsesquioxane-Containing Block Copolymers via Reversible Addition?Fragmentation Chain Transfer Polymerization and Their Self-Assembly in Aqueous Solution. Industrial & Engineering Chemistry Research 2014, 53, 10673–10680.

(404) Hong, L.; Zhang, Z.; Zhang, Y.; Zhang, W. Synthesis and Self-Assembly of Stimuli-Responsive Amphiphilic Block Copolymers Based on Polyhedral Oligomeric Silsesquioxane. Journal of Polymer Science Part A: Polymer Chemistry 2014, 52, 2669–2683.

(405) Hou, A.; Shen, H.; Zhang, K.; Xie, K. Morphological Structures of the Cellulose Hybrids Containing Polyhedral Oligomeric Silsesquioxane and Their Application for Removing C.I. Reactive Red 250. Fibers and Polymers 2014, 15, 1399–1405.

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(407) Jiang, D.; Liu, L.; Zhao, F.; Zhang, Q.; Sun, S.; He, J.; Jiang, B.; Huang, Y. Improved Interfacial Properties of Carbon Fiber/Unsaturated Polyester Composites through Coating Polyhedral Oligomeric Silsesquioxane on Carbon Fiber Surface. Fibers and Polymers 2014, 15, 566–573.

(408) Kaneko, Y.; Toyodome, H.; Mizumo, T.; Shikinaka, K.; Iyi, N. Preparation of a Sulfo-Group-Containing Rod-Like Polysilsesquioxane with a Hexagonally Stacked Structure and Its Proton Conductivity. Chem. Eur. J. 2014, 20, 9394–9399.

(409) Kim, D.-Y.; Kim, S.; Lee, S.-A.; Choi, Y.-E.; Yoon, W.-J.; Kuo, S.-W.; Hsu, C.-H.; Huang, M.; Lee, S. H.; Jeong, K.-U. Asymmetric Organic?Inorganic Hybrid Giant Molecule: Cyanobiphenyl Monosubstituted Polyhedral Oligomeric Silsesquioxane Nanoparticles for Vertical Alignment of Liquid Crystals. The Journal of Physical Chemistry C 2014, 118, 6300–6306.

(410) Li, Q.; Peng, P.; Chen, G.-X.; Yoon, S. W. High-k Polymer/Carbon Nanotube Composites Based on a Polyhedral Oligomeric Silsesquioxane Matrix Facilitated by Ionic Liquid. J. Mater. Chem. C 2014, 2, 8216–8221.

(411) Li, Q.; Bi, D.; Chen, G.-X. Gas Barrier and Biodegradable Properties of Poly(l-Lactide) Nanocomposites Compounded with Polyhedral Oligomeric Silsesquioxane Grafted Organic Montmorillonite. Journal of Polymers and the Environment 2014, 22, 471–478.

(412) Li, X.-D.; Zang, H.-P.; Wang, J.-T.; Wang, J.-F.; Zhang, H. Design of Tetraphenyl Silsesquioxane Based Covalent-Organic Frameworks as Hydrogen Storage Materials. J. Mater. Chem. A 2014, 2, 18554–18561.

(413) Li, Z.; Wu, D.; Liang, Y.; Fu, R.; Matyjaszewski, K. Synthesis of Well-Defined Microporous Carbons by Molecular-Scale Templating with Polyhedral Oligomeric Silsesquioxane Moieties. J. Am. Chem. Soc. 2014, 136, 4805–4808.

(414) Li, Z.; Yang, R. Study of the Synergistic Effect of Polyhedral Oligomeric Octadiphenylsulfonylsilsesquioxane and 9,10-Dihydro-9-Oxa-10-Phosphaphenanthrene-10-Oxide on Flame-Retarded Epoxy Resins. Polymer Degradation and Stability 2014, 109, 233–239.

(415) Liao, W.-H.; Yang, S.-Y.; Hsiao, S.-T.; Wang, Y.-S.; Li, S.-M.; Ma, C.-C. M.; Tien, H.-W.; Zeng, S.-J. Effect of Octa(Aminophenyl) Polyhedral Oligomeric Silsesquioxane Functionalized Graphene Oxide on the Mechanical and Dielectric Properties of Polyimide Composites. ACS Appl. Mater. Interfaces 2014, 6, 15802–15812.

(416) Lin, B.; Chu, F.; Yuan, N.; Shang, H.; Ren, Y.; Gu, Z.; Ding, J.; Wei, Y.; Yu, X. Phosphoric Acid Doped Polybenzimidazole/Imidazolium-Modified Silsesquioxane Hybrid Proton Conducting Membranes for Anhydrous Proton Exchange Membrane Application. Journal of Power Sources 2014, 252, 270–276.

(417) Liu, Z.; Ou, J.; Lin, H.; Wang, H.; Dong, J.; Zou, H. Preparation of Polyhedral Oligomeric Silsesquioxane-Based Hybrid Monolith by Ring-Opening Polymerization and Post-Functionalization via Thiol-Ene Click Reaction. Journal of Chromatography A 2014, 1342, 70–77.

(418) Manickam, S.; Cardiano, P.; Mineo, P. G.; Lo Schiavo, S. Star-Shaped Quaternary Alkylammonium Polyhedral Oligomeric Silsesquioxane Ionic Liquids. Eur. J. Inorg. Chem. 2014, 2014, 2704–2710.

(419) Neyertz, S.; Gopalan, P.; Brachet, P.; Kristiansen, A.; Männle, F.; Brown, D. Oxygen Transport in Amino-Functionalized Polyhedral Oligomeric Silsesquioxanes (POSS). Soft Materials 2014, 12, 113–123.

(420) Nguyen, T.-A.; Gregersen, ?yvind Weiby; M?nnle, F.; Brachet, P. Effects of Hydrophobic Polyhedral Oligomeric Silsesquioxane Coating on Water Vapour Barrier and Water Resistance Properties of Paperboard. Journal of Sol-Gel Science and Technology 2014, 69, 237–249.

(421) Panaitescu, D. M.; Frone, A. N.; Radovici, C.; Nicolae, C.; Perrin, F. X. Influence of Octyl Substituted Octakis(Dimethylsiloxy)Octasilsesquioxane on the Morphology and Thermal and Mechanical Properties of Low Density Polyethylene: Octakis(Dimethylsiloxy)Octasilsesquioxane and LDPE. Polymer International 2014, 63, 228–236.

(422) Raaijmakers, M. J. T.; Wessling, M.; Nijmeijer, A.; Benes, N. E. Hybrid Polyhedral Oligomeric Silsesquioxanes–Imides with Tailored Intercage Spacing for Sieving of Hot Gases. Chemistry of Materials 2014, 26, 3660–3664.

(423) Rodo?ek, M.; Rauter, A.; Slemenik Per?e, L.; Merl Kek, D.; ?urca Vuk, A. Vibrational and Corrosion Properties of Poly(Dimethylsiloxane)-Based Protective Coatings for AA 2024 Modified with Nanosized Polyhedral Oligomeric Silsesquioxane. Corrosion Science 2014, 85, 193–203.

(424) Sun, D.; Zhou, Z.; Chen, G.-X.; Li, Q. Regulated Dielectric Loss of Polymer Composites from Coating Carbon Nanotubes with a Cross-Linked Silsesquioxane Shell through Free-Radical Polymerization. ACS Appl. Mater. Interfaces 2014, 6, 18635–18643.

(425) Teng, C. P.; Mya, K. Y.; Win, K. Y.; Yeo, C. C.; Low, M.; He, C.; Han, M.-Y. Star-Shaped Polyhedral Oligomeric Silsesquioxane-Polycaprolactone-Polyurethane as Biomaterials for Tissue Engineering Application. NPG Asia Materials 2014, 6, e142.

(426) Wang, T.; Ding, J.; Li, J.; Liu, Y.; Hao, J. Blends of Poly(d,l-Lactide) with Polyhedral Oligomeric Silsesquioxanes-Based Biodegradable Polyester: Synthesis, Morphology, Miscibility, and Mechanical Property. Journal of Applied Polymer Science 2014, 131, n/a-n/a.

(427) Xu, Y.; Xie, J.; Chen, L.; Gao, H.; Yuan, C.; Li, C.; Luo, W.; Zeng, B.; Dai, L. Synthesis, Characterization, and Temperature-Responsive Behaviors of Novel Hybrid Amphiphilic Block Copolymers Containing Polyhedral Oligomeric Silsesquioxane: HYBRID COPOLYMER: SELF-ASSEMBLY, TEMPERATURE-RESPONSIVE BEHAVIORS. Polymers for Advanced Technologies 2014, 25, 613–623.

(428) Yun, S.; Parrondo, J.; Zhang, F.; Ramani, V. Microstructure-Property Relationships in Sulfonated Polyether Ether Ketone/Silsesquioxane Composite Membranes for Direct Methanol Fuel Cells. Journal of The Electrochemical Society 2014, 161, F815–F822.

(429) Zhang, T.; Wang, J.; Zhou, M.; Ma, L.; Yin, G.; Chen, G.; Li, Q. Influence of Polyhedral Oligomeric Silsesquioxanes (POSS) on Blue Light-Emitting Materials for OLED. Tetrahedron 2014, 70, 2478–2486.

(430) Zhang, W.; Xu, J.; Li, X.; Song, G.; Mu, J. Preparation, Characterization, and Properties of Poly(Aryl Ether Sulfone) Systems with Double-Decker Silsesquioxane in the Main Chains by Reactive Blending. Journal of Polymer Science Part A: Polymer Chemistry 2014, 52, 780–788.

(431) Zhang, W.; Zhou, Z.; Li, Q.; Chen, G.-X. Controlled Dielectric Properties of Polymer Composites from Coating Multiwalled Carbon Nanotubes with Octa-Acrylate Silsesquioxane through Diels?Alder Cycloaddition and Atom Transfer Radical Polymerization. Industrial & Engineering Chemistry Research 2014, 53, 6699–6707.

(432) Zhang, X.; Li, C.; Hu, Y.; Liu, R.; He, L.; Fang, S. A Novel Temperature and PH Dual-Responsive Hybrid Hydrogel with Polyhedral Oligomeric Silsesquioxane as Crosslinker: Synthesis, Characterization and Drug Release Properties. Polymer International 2014, 63, 2030–2041.

(433) Zhou, W.; Shi, J.; Yuan, S.; Chen, Y. Crystallization and Shear-Induced Formation of Organogels in Novel Poly[(Butylene Succinate)- Co -Diolisobutyl]-[Polyhedral Oligomeric Silsesquioxane] Copolyesters: Organogels in Novel Copolyesters. Polymer International 2014, 63, 626–632.

(434) Asuncion, M. Z.; David J. KRUG, I.; Abu-Seir, H. W.; Laine, R. M. Facile Thiol-Ene Reactions of Vinyl T10/T12 Silsesquioxanes for Controlled Refractive Indices for Transparent Fiber Glass Reinforced Composites. Journal of the Ceramic Society of Japan 2015, 123, 725–731.

(435) Chen, G.; Zhou, Y.; Wang, X.; Li, J.; Xue, S.; Liu, Y.; Wang, Q.; Wang, J. Construction of Porous Cationic Frameworks by Crosslinking Polyhedral Oligomeric Silsesquioxane Units with N-Heterocyclic Linkers. Scientific Reports 2015, 5, 11236.

(436) Croissant, J. G.; Mauriello-Jimenez, C.; Maynadier, M.; Cattoën, X.; Wong Chi Man, M.; Raehm, L.; Mongin, O.; Blanchard-Desce, M.; Garcia, M.; Gary-Bobo, M.; Maillard, P.; Durand, J.-O. Synthesis of Disulfide-Based Biodegradable Bridged Silsesquioxane Nanoparticles for Two-Photon Imaging and Therapy of Cancer Cells. Chem. Commun. 2015, 51, 12324–12327.

(437) Deon, M.; Caldas, E. M.; da Rosa, D. S.; de Menezes, E. W.; Dias, S. L. P.; Pereira, M. B.; Costa, T. M. H.; Arenas, L. T.; Benvenutti, E. V. Mesoporous Silica Xerogel Modified with Bridged Ionic Silsesquioxane Used to Immobilize Copper Tetrasulfonated Phthalocyanine Applied to Electrochemical Determination of Dopamine. Journal of Solid State Electrochemistry 2015, 19, 2095–2105.

(438) Fatieiev, Y.; Croissant, J. G.; Alsaiari, S.; Moosa, B. A.; Anjum, D. H.; Khashab, N. M. Photoresponsive Bridged Silsesquioxane Nanoparticles with Tunable Morphology for Light-Triggered Plasmid DNA Delivery. ACS Appl. Mater. Interfaces 2015, 7, 24993–24997.

(439) Freitas, Vânia. T.; Fu, L.; Cojocariu, A. M.; Cattoën, X.; Bartlett, J. R.; Le Parc, R.; Bantignies, J.-L.; Wong Chi Man, M.; André, P. S.; Ferreira, R. A. S.; Carlos, L. D. Eu3+-Based Bridged Silsesquioxanes for Transparent Luminescent Solar Concentrators. ACS Appl. Mater. Interfaces 2015, 7, 8770–8778.

(440) Gnanasekaran, D.; Shanavas, A.; Focke, W. W.; Sadiku, R. Polyhedral Oligomeric Silsesquioxane/Polyamide Bio-Nanocomposite Membranes: Structure-Gas Transport Properties. RSC Adv. 2015, 5, 11272–11283.

(441) Groch, P.; Dziubek, K.; Czaja, K. Silsesquioxanes and Their Application in the Synthesis of Polymeric Materials. Polimery 2015, 60, 219–231.

(442) Han, D.; Guo, Q.-Y.; Zhang, W.-B.; Liu, L.-X.; Fu, Q. Preparation and Properties of Polystyrene Nanocomposites Containing Dumbbell-Shaped Molecular Nanoparticles Based on Polyhedral Oligomeric Silsesquioxane and [60]Fullerene. RSC Adv. 2015, 5, 70051–70058.

(443) Huang, Y.; Gong, S.-D.; Huang, R.; Cao, H.-J.; Lin, Y.-H.; Yang, M.; Li, X. Polyhedral Oligomeric Silsesquioxane Containing Gel Polymer Electrolyte Based on a PMMA Matrix. RSC Adv. 2015, 5, 45908–45918.

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(445) Janaszewska, A.; Gradzinska, K.; Marcinkowska, M.; Klajnert-Maculewicz, B.; Stanczyk, W. A. In Vitro Studies of Polyhedral Oligo Silsesquioxanes: Evidence for Their Low Cytotoxicity. Materials 2015, 8, 6062–6070.

(446) Kataoka, S.; Banerjee, S.; Kawai, A.; Kamimura, Y.; Choi, J.-C.; Kodaira, T.; Sato, K.; Endo, A. Layered Hybrid Perovskites with Micropores Created by Alkylammonium Functional Silsesquioxane Interlayers. J. Am. Chem. Soc. 2015, 137, 4158–4163.

(447) Kim, H.-U.; Yoon, K. H. Morphology and Thermal Properties of PET Nanocomposite Fibers by Modified Amine-Polyhedral Oligomeric Silsesquioxane. Composites Science and Technology 2015, 121, 89–94.

(448) Lee, B. K.; Baek, I.-B.; Kim, Y.; Jang, W. I.; Yoon, Y. S.; Yu, H. Y. Fabrication of Large-Area Hierarchical Structure Array Using Siliconized-Silsesquioxane as a Nanoscale Etching Barrier. ACS Appl. Mater. Interfaces 2015, 7, 13490–13496.

(449) Li, X.; Hao, J.; Jiang, Q.; Mu, J.; Jiang, Z. Phosphorus-Containing Polyhedral Oligomeric Silsesquioxane/Polyimides Hybrid Materials with Low Dielectric Constant and Low Coefficients of Thermal Expansion. J. Appl. Polym. Sci. 2015, 132, n/a-n/a.

(450) Ni, L.; Chemtob, A.; Croutxé-Barghorn, C.; Dietlin, C.; Brendlé, J.; Rigolet, S.; Vidal, L.; Dieterlen, A.; Maalouf, E.; Haeberlé, O. Photoinduced Self-Assembly of Carboxylic Acid-Terminated Lamellar Silsesquioxane: Highly Functional Films for Attaching and Patterning Amino-Based Ligands. RSC Adv. 2015, 5, 45703–45709.

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(453) Periyasamy, T.; Asrafali, S. P.; Muthusamy, S. New Benzoxazines Containing Polyhedral Oligomeric Silsesquioxane from Eugenol, Guaiacol and Vanillin. New J. Chem. 2015, 39, 1691–1702.

(454) Ryu, S.-W.; Choi, H.-J.; Choo, S.; Kim, C.-H.; Lee, H. Fabrication of Rigid Stamp on a Cylindrical Substrate Using Hydrogen Silsesquioxane/ZrO2 Nanoparticle Composite Material for Roll-to-Roll Nanoimprinting Process. Journal of Sol-Gel Science and Technology 2015, 73, 628–633.

(455) Wang, K.; Guan, X.; Chai, S.; Zou, Q.; Zhang, X.; Zhang, J. A Novel, Molecularly Imprinted Polymer Sensor Made Using an Oligomeric Methyl Silsesquioxane?TiO2 Composite Sol on a Glassy Carbon Electrode for the Detection of Procainamide Hydrochloride. Biosensors and Bioelectronics 2015, 64, 94–101.

(456) Wang, P.; Tang, Y.; Yu, Z.; Gu, J.; Kong, J. Advanced Aromatic Polymers with Excellent Antiatomic Oxygen Performance Derived from Molecular Precursor Strategy and Copolymerization of Polyhedral Oligomeric Silsesquioxane. ACS Appl. Mater. Interfaces 2015, 7, 20144–20155.

(457) Wang, W.-J.; Hai, X.; Mao, Q.-X.; Chen, M.-L.; Wang, J.-H. Polyhedral Oligomeric Silsesquioxane Functionalized Carbon Dots for Cell Imaging. ACS Appl. Mater. Interfaces 2015, 7, 16609–16616.

(458) Wang, Z.; Wang, D.; Qian, Z.; Guo, J.; Dong, H.; Zhao, N.; Xu, J. Robust Superhydrophobic Bridged Silsesquioxane Aerogels with Tunable Performances and Their Applications. ACS Appl. Mater. Interfaces 2015, 7, 2016–2024.

(459) Wang, Z.; Wu, W.; Zhong, Y.; Ruan, M.; Hui, L. L. Flame-Retardant Materials Based on Phosphorus-Containing Polyhedral Oligomeric Silsesquioxane and Bismaleimide/Diallylbisphenol a with Improved Thermal Resistance and Dielectric Properties. Journal of Applied Polymer Science 2015, n/a-n/a.

(460) Zhang, C.; Zhang, C.; Sun, J.; Ding, R.; Zhang, Q.; Xu, Y. A Double-Layer Moisture Barrier & Antireflective Film Based on Bridged Polysilsesquioxane and Porous Silica. RSC Adv. 2015, 5, 56998–57005.

(461) Zhang, N.; Zhang, L.; Qiao, X.; Wang, Y.; Yan, H.; Bai, L. Facile One-Pot Preparation of an Imidazolium Embedded C8 Hybrid Monolith Using Polyhedral Oligomeric Silsesquioxane for Capillary Liquid Chromatography. RSC Adv. 2015, 5, 91436–91440.

(462) Bele, A.; Dascalu, M.; Tugui, C.; Iacob, M.; Racles, C.; Sacarescu, L.; Cazacu, M. Dielectric Silicone Elastomers Filled with in Situ Generated Polar Silsesquioxanes: Preparation, Characterization and Evaluation of Electromechanical Performance. Materials & Design 2016, 106, 454–462.

(463) Bu, X.; Zhou, Y.; Li, C.; Huang, F. Octakis(Ethynyldimethylsiloxy) Silsesquioxane: Synthesis and Application in Poly(Silicane Arylacetylene) Resin. J. Appl. Polym. Sci. 2016, 133, n/a-n/a.

(464) Cabrera-González, J.; Sánchez-Arderiu, V.; Viñas, C.; Parella, T.; Teixidor, F.; Núñez, R. Redox-Active Metallacarborane-Decorated Octasilsesquioxanes. Electrochemical and Thermal Properties. Inorg. Chem. 2016, 55, 11630–11634.

(465) Czarnecka-Komorowska, D.; Sterzynski, T.; Dutkiewicz, M. Polyoxymethylene/Polyhedral Oligomeric Silsesquioxane Composites: Processing, Crystallization, Morphology and Thermo-Mechanical Behavior. IPP 2016, 31, 598–606.

(466) Deshmukh, A.; Chiu, C.; Chen, Y.-W.; Kuo, J.-L. Tunable Gravimetric and Volumetric Hydrogen Storage Capacities in Polyhedral Oligomeric Silsesquioxane Frameworks. ACS Appl. Mater. Interfaces 2016, 8, 25219–25228.

(467) Dopierała, K.; Bojakowska, K.; Karasiewicz, J.; Maciejewski, H.; Prochaska, K. Interfacial Behaviour of Cubic Silsesquioxane and Silica Nanoparticles in Langmuir and Langmuir–Blodgett Films. RSC Adv. 2016, 6, 94934–94941.

(468) Gao, L.; Wei, Y. Fabrication of Boronate-Decorated Polyhedral Oligomeric Silsesquioxanes Grafted Cotton Fiber for the Selective Enrichment of Nucleosides in Urine. J. Sep. Science 2016, 39, 2365–2373.

(469) Ge, M.; Liu, H. A Silsesquioxane-Based Thiophene-Bridged Hybrid Nanoporous Network as a Highly Efficient Adsorbent for Wastewater Treatment. J. Mater. Chem. A 2016, 4, 16714–16722.

(470) Han, Z.; Xi, Y.; Kwon, Y. Thermal Stability and Ablation Behavior of Modified Polydimethylsiloxane-Based Polyurethane Composites Reinforced with Polyhedral Oligomeric Silsesquioxane. J Nanosci Nanotechnol 2016, 16, 1928–1933.

(471) Hayashi, E.; Shimokawa, T. Synthesis and Characterization of Hydrophobic and Mesoporous Silicate–Silsesquioxane Hybrid Copolymers. Microporous and Mesoporous Materials 2016, 219, 178–185.

(472) Huang, H.; Chen, B.; Wang, Z.; Hung, T. F.; Susha, A. S.; Zhong, H.; Rogach, A. L. Water Resistant CsPbX 3 Nanocrystals Coated with Polyhedral Oligomeric Silsesquioxane and Their Use as Solid State Luminophores in All-Perovskite White Light-Emitting Devices. Chemical Science 2016, 7, 5699–5703.

(473) Jiang, C.; Yang, W.; Liu, H. Hybrid Azobenzene-Doped Nanoporous Polymers Derived from Cubic Octavinylsilsesquioxane. Russian Chemical Bulletin 2016, 65, 1076–1085.

(474) Kaneko, Y.; Imamura, H.; Sugioka, T.; Sumida, Y. Preparation and Thermal Properties of Soluble Polysilsesquioxanes Containing Hydrophobic Side-Chain Groups and Their Hybridization with Organic Polymers. Polymer 2016, 92, 250–255.

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(476) Miyauchi, S.; Imoto, H.; Naka, K. Fabrication of Polymer-Calcite Composite Thin Films by Phase Transition of Vaterite Composite Particles with Octacarboxy-Terminated T8-Caged Silsesquioxane. Polym J 2016, 48, 1019–1027.

(477) Na, W.; Lee, A. S.; Lee, J. H.; Hwang, S. S.; Kim, E.; Hong, S. M.; Koo, C. M. Lithium Dendrite Suppression with UV-Curable Polysilsesquioxane Separator Binders. ACS Appl. Mater. Interfaces 2016, 8, 12852–12858.

(478) Sans, M.; Illa, O.; Ortuño, R. M. Organobridged Silsesquioxanes Based on Cyclobutane Diamines: Influence of the Stereochemistry on the Morphology of the Materials. Tetrahedron 2016, 72, 2913–2919.

(479) Shen, R.; Feng, S.; Liu, H. Silsesquioxane-Based Luminescent PMMA Nanocomposites. RSC Adv. 2016, 6, 59305–59312.

(480) Shimizu, T.; Kanamori, K.; Maeno, A.; Kaji, H.; Doherty, C. M.; Falcaro, P.; Nakanishi, K. Transparent, Highly Insulating Polyethyl- and Polyvinylsilsesquioxane Aerogels: Mechanical Improvements by Vulcanization for Ambient Pressure Drying. Chemistry of Materials 2016, 28, 6860–6868.

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(526) Synthesis-and-Influence-of-Sodium-Benzoate-Silsesquioxane-Based-Nucleating-a.Html.

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