journal article·2025-12Open access

Self-healing materials based on dynamic properties of siloxane networks

Taiki Hayashi, Atsushi Shimojima

Abstract

Abstract Siloxane-based materials have a wide range of applications due to their high thermal and chemical stability, as well as tunable properties and functions achieved by incorporating organic groups via Si–C bonds. Imparting self-healing abilities to siloxane-based materials represents an effective strategy for enhancing their lifetime and reliability. Both extrinsic and intrinsic self-healing systems in siloxane-based materials have been extensively studied. This review focuses on recent progress in the intrinsic self-healing of siloxane-based materials, particularly highlighting research on healing mechanisms through the use of siloxane bonds as dynamic bonds. Additionally, new self-healing systems based on mesoscale structural control of silica and silsesquioxane are introduced. Graphical Abstract
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Research context

OpenAlex topics: Polymer composites and self-healing · Silicone and Siloxane Chemistry · Synthesis and properties of polymers

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References (100+)

Show source-provided references
1. Yilgör E, Yilgör I (2014) Silicone containing copolymers: Synthesis, properties and applications. Prog Polym Sci 39(6):1165–119510.1016/j.progpolymsci.2013.11.003 ↗
2. Mazurek P, Vudayagiri S, Skov AL (2019) How to tailor flexible silicone elastomers with mechanical integrity: A tutorial review. Chem Soc Rev 48(6):1448–146410.1039/C8CS00963E ↗
3. Brinker CJ, Scherer GW (1990) Sol-gel science: The physics and chemistry of sol-gel processing. Academic Press, Inc., San Diego.
4. Baney RH, Itoh M, Sakakibara A, Suzuki T (1995) Silsesquioxanes. Chem Rev 95(5):1409–143010.1021/cr00037a012 ↗
5. Sanchez C, Julián B, Belleville P, Popall M (2005) Applications of hybrid organic–inorganic nanocomposites. J Mater Chem 15(35-36):3559–359210.1039/b509097k ↗
6. Sanchez C, Belleville P, Popall M, Nicole L (2011) Applications of advanced hybrid organic–inorganic nanomaterials: From laboratory to market. Chem Soc Rev 40(2):696–75310.1039/c0cs00136h ↗
7. Ciriminna R, Fidalgo A, Pandarus V, Béland F, Ilharco LM, Pagliaro M (2013) The sol–gel route to advanced silica-based materials and recent applications. Chem Rev 113(8):6592–662010.1021/cr300399c ↗
8. Yang Y, Urban MW (2013) Self-healing polymeric materials. Chem Soc Rev 42(17):7446–746710.1039/c3cs60109a ↗
9. Hager MD, Greil P, Leyens C, van der Zwaag S, Schubert US (2010) Self-healing materials. Adv Mater 22(47):5424–543010.1002/adma.201003036 ↗
10. Ghosh SK (2009) Self-healing materials: Fundamentals, design strategies, and applications. WILEY-VCH Verlag GmbH & Co, KGaA, Weinheim
11. Keller MW, White SR, Sottos NR (2007) A self-healing poly(dimethyl siloxane) elastomer. Adv Func Mater 17(14):2399–240410.1002/adfm.200700086 ↗
12. Wang J, Lv C, Li Z, Zheng J (2018) Facile preparation of polydimethylsiloxane elastomer with self-healing property and remoldability based on Diels–Alder chemistry. Macromol Mater Eng 303(6):180008910.1002/mame.201800089 ↗
13. Yan Q, Zhao L, Cheng Q, Zhang T, Jiang B, Song Y, Huang Y (2019) Self-healing polysiloxane elastomer based on integration of covalent and reversible networks. Ind Eng Chem Res 58(47):21504–2151210.1021/acs.iecr.9b04355 ↗
14. Yilmaz D, Lansade D, Lewandowski S, Perraud S, Llevot A, Carlotti S (2022) Combination of permanent hydrosilylation and reversible Diels–Alder reactions for self-healing poly(dimethylsiloxane) materials with enhanced ageing properties. Mater Today Chem 24:10086010.1016/j.mtchem.2022.100860 ↗
15. Zhang B, Zhang P, Zhang H, Yan C, Zheng Z, Wu B, Yu Y (2017) A transparent, highly stretchable, autonomous self-healing poly(dimethyl siloxane) elastomer. Macromol Rapid Commun 38(15):170011010.1002/marc.201700110 ↗
16. Qian Y, Dong F, Guo L, Lu S, Xu X, Liu H (2023) Self-healing and reprocessable terpene polysiloxane-based poly(thiourethane-urethane) material with reversible thiourethane bonds. Biomacromolecules 24(3):1184–119310.1021/acs.biomac.2c01230 ↗
17. Lai J-C, Mei J-F, Jia X-Y, Li C-H, You X-Z, Bao Z (2016) A stiff and healable polymer based on dynamic-covalent boroxine bonds. Adv Mater 28(37):8277–828210.1002/adma.201602332 ↗
18. Wang P, Wang Z, Liu L, Ying G, Cao W, Zhu J (2023) Self-healable and reprocessable silicon elastomers based on imine–boroxine bonds for flexible strain sensor. Molecules 28(16):604910.3390/molecules28166049 ↗
19. Wang P, Wang Z, Cao W, Zhu J (2024) Facile preparation of a transparent, self-healing, and recyclable polysiloxane elastomer based on a dynamic imine and boroxine bond. Polymers 16(9):126210.3390/polym16091262 ↗
20. Tang M, Zheng P, Wang K, Qin Y, Jiang Y, Cheng Y, Li Z, Wu L (2019) Autonomous self-healing, self-adhesive, highly conductive composites based on a silver-filled polyborosiloxane/polydimethylsiloxane double-network elastomer. J Mater Chem A 7(48):27278–2728810.1039/C9TA09158K ↗
21. Lee J, Jing BB, Porath LE, Sottos NR, Evans CM (2020) Shock wave energy dissipation in catalyst-free poly(dimethylsiloxane) vitrimers. Macromolecules 53(12):4741–474710.1021/acs.macromol.0c00784 ↗
22. Drozdov FV, Manokhina EA, Vu TD, Muzafarov AM (2022) Polyborosiloxanes (PBS): Evolution of approaches to the synthesis and the prospects of their application. Polymers 14(22):482410.3390/polym14224824 ↗
23. D’Ambra CA, Getty PT, Eom T, Czuczola M, Murphy EA, Biswas S, Abdilla A, Mecca JM, Bekemeier TD, Swier S, Fielitz A, Hawker CJ, Bates CM (2024) Facile preparation of tunable polyborosiloxane networks via hydrosilylation. Chem Mater 36(12):5935–594210.1021/acs.chemmater.4c00224 ↗
24. Krishnakumar B, Singh M, Parthasarthy V, Park C, Sahoo NG, Yun GJ, Rana S (2020) Disulfide exchange assisted self-healing epoxy/pdms/graphene oxide nanocomposites. Nanoscale Adv 2(7):2726–273010.1039/D0NA00282H ↗
25. Liu Y, Yuan J, Zhang K, Guo K, Yuan L, Wu Y, Gao C (2020) A novel type of self-healing silicone elastomers with reversible cross-linked network based on the disulfide, hydrogen and metal-ligand bonds. Prog Org Coat 144:10566110.1016/j.porgcoat.2020.105661 ↗
26. Zhang T, Su H, Shi X, Li C (2022) Self-healing siloxane elastomers constructed by hierarchical covalent crosslinked networks and reversible dynamic bonds for flexible electronics. J Mater Sci 57(22):10444–1045610.1007/s10853-022-07293-7 ↗
27. Wang S-J, Wang L, Su H-Z, Wu Z-C, Zhang Q-G, Fan W, Jing X-L (2024) Room-temperature self-healing and recyclable PDMS elastomers with superior mechanical properties for triboelectric nanogenerators. Chin J Polym Sci 42(10):1566–157710.1007/s10118-024-3178-5 ↗
28. Utrera-Barrios S, Verdejo R, López-Manchado MA, Hernández Santana M (2020) Evolution of self-healing elastomers, from extrinsic to combined intrinsic mechanisms: A review. Mater Horiz 7(11):2882–290210.1039/D0MH00535E ↗
29. Yi B, Wang S, Hou C, Huang X, Cui J, Yao X (2021) Dynamic siloxane materials: From molecular engineering to emerging applications. Chem Eng J 405:12702310.1016/j.cej.2020.127023 ↗
30. Deriabin KV, Filippova SS, Islamova RM (2023) Self-healing silicone materials: Looking back and moving forward. Biomimetics 8(3):28610.3390/biomimetics8030286 ↗
31. Kowalewska A, Majewska-Smolarek K (2024) Synergistic self-healing enhancement in multifunctional silicone elastomers and their application in smart materials. Polymers 16(4):48710.3390/polym16040487 ↗
32. Li C-H, Wang C, Keplinger C, Zuo J-L, Jin L, Sun Y, Zheng P, Cao Y, Lissel F, Linder C, You X-Z, Bao Z (2016) A highly stretchable autonomous self-healing elastomer. Nat Chem 8(6):618–62410.1038/nchem.2492 ↗
33. Miwa Y, Taira K, Kurachi J, Udagawa T, Kutsumizu S (2019) A gas-plastic elastomer that quickly self-heals damage with the aid of CO2 gas. Nat Commun 10(1):182810.1038/s41467-019-09826-2 ↗
34. Yin Q, Tu S, Chen M, Wu L (2020) Self-detecting and self-healing reinforce elastomer doped with aggregation-induced emission molecules. Macromol Mater Eng 305(4):200001310.1002/mame.202000013 ↗
35. Nowacka M, Kowalewska A (2022) Self-healing silsesquioxane-based materials. Polymers 14(9):186910.3390/polym14091869 ↗
36. Xu Z, Zhao Y, Wang X, Lin T (2013) A thermally healable polyhedral oligomeric silsesquioxane (POSS) nanocomposite based on Diels–Alder chemistry. Chem Commun 49(60):6755–675710.1039/c3cc43432j ↗
37. Levitsky MM, Bilyachenko AN (2016) Modern concepts and methods in the chemistry of polyhedral metallasiloxanes. Coord Chem Rev 306:235–26910.1016/j.ccr.2015.07.007 ↗
38. Laine RM (2005) Nanobuilding blocks based on the [OSiO1.5]x (x = 6, 8, 10) silsesquioxanes. J Mater Chem 15(35-36):3725–374410.1039/b506815k ↗
39. Takahashi N, Kuroda K (2011) Materials design of layered silicates through covalent modification of interlayer surfaces. J Mater Chem 21(38):14336–1435310.1039/c1jm10460h ↗
40. Kantor SW, Grubb WT, Osthoff RC (1954) The mechanism of the acid- and base-catalyzed equilibration of siloxanes. J Am Chem Soc 76(20):5190–519710.1021/ja01649a076 ↗
41. Hurd DT, Osthoff RC, Corrin ML (1954) The mechanism of the base-catalyzed rearrangement of organopolysiloxanes1. J Am Chem Soc 76(1):249–25210.1021/ja01630a064 ↗
42. Osthoff RC, Bueche AM, Grubb WT (1954) Chemical stress-relaxation of polydimethylsiloxane elastomers. J Am Chem Soc 76(18):4659–466310.1021/ja01647a052 ↗
43. Zheng P, McCarthy TJ (2012) A surprise from 1954: Siloxane equilibration is a simple, robust, and obvious polymer self-healing mechanism. J Am Chem Soc 134(4):2024–202710.1021/ja2113257 ↗
44. Schmolke W, Perner N, Seiffert S (2015) Dynamically cross-linked polydimethylsiloxane networks with ambient-temperature self-healing. Macromolecules 48(24):8781–878810.1021/acs.macromol.5b01666 ↗
45. Gilbert AR, Kantor SW (1959) Transient catalysts for the polymerization of organosiloxanes. J Polym Sci 40(136):35–5810.1002/pol.1959.1204013603 ↗
46. Li X, Yu R, Zhao T, Zhang Y, Yang X, Zhao X, Huang W (2018) A self-healing polysiloxane elastomer based on siloxane equilibration synthesized through amino-ene michael addition reaction. Eur Polym J 108:399–40510.1016/j.eurpolymj.2018.09.021 ↗
47. von Szczepanski J, Danner PM, Opris DM (2022) Self-healable, self-repairable, and recyclable electrically responsive artificial muscles. Adv Sci 9(22):220215310.1002/advs.202202153 ↗
48. Lee W, Kim H, Han I-S, Chae C-G, Park S, Kim D-G, Kim YS (2024) Reprocessable and 3D printable polydimethylsiloxane by dynamic siloxane bond exchange. MRS Commun 14(4):527–53310.1557/s43579-024-00553-4 ↗
49. Berkefeld A, Guerra CF, Bertermann R, Troegel D, Daiß JO, Stohrer J, Bickelhaupt FM, Tacke R (2014) Silicon α-effect: A systematic experimental and computational study of the hydrolysis of Cα- and Cγ-functionalized alkoxytriorganylsilanes of the formula type ROSiMe2(CH2)nX (R = Me, Et; n = 1, 3; X = functional group). Organometallics 33(11):2721–273710.1021/om500073m ↗
50. Nishimura Y, Chung J, Muradyan H, Guan Z (2017) Silyl ether as a robust and thermally stable dynamic covalent motif for malleable polymer design. J Am Chem Soc 139(42):14881–1488410.1021/jacs.7b08826 ↗
51. Tretbar CA, Neal JA, Guan Z (2019) Direct silyl ether metathesis for vitrimers with exceptional thermal stability. J Am Chem Soc 141(42):16595–1659910.1021/jacs.9b08876 ↗
52. Saed MO, Terentjev EM (2020) Siloxane crosslinks with dynamic bond exchange enable shape programming in liquid-crystalline elastomers. Sci Rep. 10(1):660910.1038/s41598-020-63508-4 ↗
53. Capelot M, Montarnal D, Tournilhac F, Leibler L (2012) Metal-catalyzed transesterification for healing and assembling of thermosets. J Am Chem Soc 134(18):7664–766710.1021/ja302894k ↗
54. Wu X, Yang X, Yu R, Zhao X-J, Zhang Y, Huang W (2018) A facile access to stiff epoxy vitrimers with excellent mechanical properties via siloxane equilibration. J Mater Chem A 6(22):10184–1018810.1039/C8TA02102C ↗
55. Xu W, Pan Y, Deng J, Yin L, Zheng Z, Ding X (2021) Reprocessable and self-healing shape memory epoxy resin based on biphenyl mesogen and siloxane. Macromol Chem Phys 222(23):210029010.1002/macp.202100290 ↗
56. Putnam-Neeb AA, Kaiser JM, Hubbard AM, Street DP, Dickerson MB, Nepal D, Baldwin LA (2022) Self-healing and polymer welding of soft and stiff epoxy thermosets via silanolates. Adv Compos Hybrid Mater 5(4):3068–308010.1007/s42114-022-00558-4 ↗
57. Tilgner IC, Fischer P, Bohnen FM, Rehage H, Maier WF (1995) Effect of acidic, basic and fluoride-catalyzed sol-gel transitions on the preparation of sub-nanostructured silica. Microporous Mater 5(1):77–9010.1016/0927-6513(95)00045-B ↗
58. Hu N-h, Furgal JC (2020) R-silsesquioxane-based network polymers by fluoride catalyzed synthesis: An investigation of cross-linker structure and its influence on porosity. Materials 13(8):184910.3390/ma13081849 ↗
59. Bassindale AR, Liu Z, MacKinnon IA, Taylor PG, Yang Y, Light ME, Horton PN, Hursthouse MB (2003) A higher yielding route for T8 silsesquioxane cages and X-ray crystal structures of some novel spherosilicates. Dalton Trans (14):2945–294910.1039/b302950f ↗
60. Bassindale AR, Chen H, Liu Z, MacKinnon IA, Parker DJ, Taylor PG, Yang Y, Light ME, Horton PN, Hursthouse MB (2004) 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. J Organomet Chem 689(21):3287–330010.1016/j.jorganchem.2004.06.063 ↗
61. Laird M, Van der Lee A, Dumitrescu DG, Carcel C, Ouali A, Bartlett JR, Unno M, Wong Chi Man M (2020) Styryl-functionalized cage silsesquioxanes as nanoblocks for 3-D assembly. Organometallics 39(10):1896–190610.1021/acs.organomet.0c00119 ↗
62. Laird M, Herrmann N, Ramsahye N, Totée C, Carcel C, Unno M, Bartlett JR, Wong Chi Man M (2021) Large polyhedral oligomeric silsesquioxane cages: The isolation of functionalized poss with an unprecedented Si18O27 core. Angew Chem Int Ed 60(6):3022–302710.1002/anie.202010458 ↗
63. Rey N, Carenco S, Carcel C, Ouali A, Portehault D, Wong Chi Man M, Sanchez C (2019) Dumbbell-shaped T8-poss with functional organic linkers. Eur J Inorg Chem 2019(27):3148–315610.1002/ejic.201900284 ↗
64. Yatomi M, Koike M, Rey N, Murakami Y, Saito S, Wada H, Shimojima A, Portehault D, Carenco S, Sanchez C, Carcel C, Wong Chi Man M, Kuroda K (2021) Interlayer silylation of layered octosilicate with organoalkoxysilanes: Effects of tetrabutylammonium fluoride as a catalyst and the functional groups of silanes. Eur J Inorg Chem 2021(19):1836–184510.1002/ejic.202100050 ↗
65. Suzuki M, Hayashi T, Hikino T, Kishi M, Matsuno T, Wada H, Kuroda K, Shimojima A (2023) Integrated extrinsic and intrinsic self-healing of polysiloxane materials by cleavable molecular cages encapsulating fluoride ions. Adv Sci 10(27):230365510.1002/advs.202303655 ↗
66. Nguyen du T, Leho YT, Esser-Kahn AP (2013) Process of making three-dimensional microstructures using vaporization of a sacrificial component. J Vis Exp (81):e5045910.3791/50459-v ↗
67. Kleiman M, Ryu KA, Esser-Kahn AP (2016) Determination of factors influencing the wet etching of polydimethylsiloxane using tetra-n-butylammonium fluoride. Macromol Chem Phys 217(2):284–29110.1002/macp.201500225 ↗
68. Brubaker KS, Kleiman M, Hernandez L, Bhattacharjee A, Esser-Kahn AP (2018) Structural remodeling of polymeric material via diffusion controlled polymerization and chain scission. Chem Mater 30(22):8126–813310.1021/acs.chemmater.8b02293 ↗
69. Ronchi M, Sulaiman S, Boston NR, Laine RM (2010) Fluoride catalyzed rearrangements of polysilsesquioxanes, mixed Me, vinyl T8, Me, vinyl T10 and T12 cages. Appl Organomet Chem 24(8):551–55710.1002/aoc.1579 ↗
70. Asuncion MZ, Laine RM (2010) Fluoride rearrangement reactions of polyphenyl- and polyvinylsilsesquioxanes as a facile route to mixed functional phenyl, vinyl T10 and T12 silsesquioxanes. J Am Chem Soc 132(11):3723–373610.1021/ja9087743 ↗
71. Jung JH, Laine RM (2011) Beads on a chain (BOX) polymers formed from the reaction of [NH2PhSiO1.5]x[PhSiO1.5]10–x and [NH2PhSiO1.5]x[PhSiO1.5]12–x mixtures (x = 2–4) with the diglycidyl ether of bisphenol A. Macromolecules 44(18):7263–727210.1021/ma201032r ↗
72. Hwan Jung J, Furgal JC, Goodson III T, Mizumo T, Schwartz M, Chou K, Vonet J-F, Laine RM (2012) 3-D molecular mixtures of catalytically functionalized [vinylSiO1.5]10/[vinylSiO1.5]12. Photophysical characterization of second generation derivatives. Chem Mater 24(10):1883–189510.1021/cm300587s ↗
73. Furgal JC, Jung JH, Clark S, Goodson III T, Laine RM (2013) Beads on a chain (BoC) phenylsilsesquioxane (SQ) polymers via F– catalyzed rearrangements and admet or reverse heck cross-coupling reactions: Through chain, extended conjugation in 3-d with potential for dendronization. Macromolecules 46(19):7591–760410.1021/ma401423f ↗
74. Furgal JC, Goodson Iii T, Laine RM (2016) D5h [phSiO1.5]10 synthesis via F− catalyzed rearrangement of [PhSiO1.5]n. An experimental/computational analysis of likely reaction pathways. Dalton Trans 45(3):1025–103910.1039/C5DT04182A ↗
75. Furgal JC, Yamane H, Odykirk TR, Yi E, Chujo Y, Laine RM (2018) High surface area, thermally stable, hydrophobic, microporous, rigid gels generated at ambient from MeSi(OEt)3/(EtO)3SiCH2CH2Si(OEt)3 mixtures by F−-catalyzed hydrolysis. Chem Eur J 24(1):274–28010.1002/chem.201704941 ↗
76. Takahashi A, Okada T, Nakano K, Ishida Y, Kameyama A (2021) Poss cage-scrambling-induced gelation of poss-pendant random copolymers catalyzed by fluoride anions. Polym J 53(11):1213–122210.1038/s41428-021-00523-w ↗
77. Bassindale AR, Pourny M, Taylor PG, Hursthouse MB, Light ME (2003) Fluoride-ion encapsulation within a silsesquioxane cage. Angew Chem Int Ed 42(30):3488–349010.1002/anie.200351249 ↗
78. Bassindale AR, Parker DJ, Pourny M, Taylor PG, Horton PN, Hursthouse MB (2004) 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 23(19):4400–440510.1021/om049928g ↗
79. Anderson SE, Bodzin DJ, Haddad TS, Boatz JA, Mabry JM, Mitchell C, Bowers MT (2008) Structural investigation of encapsulated fluoride in polyhedral oligomeric silsesquioxane cages using ion mobility mass spectrometry and molecular mechanics. Chem Mater 20(13):4299–430910.1021/cm800058z ↗
80. El Aziz Y, Bassindale AR, Taylor PG, Horton PN, Stephenson RA, Hursthouse MB (2012) Facile synthesis of novel functionalized silsesquioxane nanostructures containing an encapsulated fluoride anion. Organometallics 31(17):6032–604010.1021/om300277g ↗
81. Taylor PG, Bassindale AR, El Aziz Y, Pourny M, Stevenson R, Hursthouse MB, Coles SJ (2012) Further studies of fluoride ion entrapment in octasilsesquioxane cages; X-ray crystal structure studies and factors that affect their formation. Dalton Trans 41(7):2048–205910.1039/C1DT11340B ↗
82. El Aziz Y, Taylor PG, Bassindale AR, Coles SJ, Pitak MB (2016) Synthesis and structures of novel molecular ionic compounds based on encapsulation of anions and cations. Organometallics 35(24):4004–401310.1021/acs.organomet.6b00565 ↗
83. Heeley E, El Aziz Y, Ellingford C, Jetybayeva A, Wan C, Crabb E, Taylor PG, Bassindale A (2019) Self-assembly of fluoride-encapsulated polyhedral oligomeric silsesquioxane (POSS) nanocrystals. CrystEngComm 21(4):710–72310.1039/C8CE01750F ↗
84. Laird M, Totée C, Gaveau P, Silly G, Van der Lee A, Carcel C, Unno M, Bartlett JR, Wong Chi Man M (2021) Functionalised polyhedral oligomeric silsesquioxane with encapsulated fluoride – first observation of fluxional Si⋯F interactions in POSS. Dalton Trans 50(1):81–8910.1039/D0DT03057K ↗
85. Laird M, Gaveau P, Trens P, Carcel C, Unno M, Bartlett JR, Wong Chi Man M (2021) Post-synthesis modification of functionalised polyhedral oligomeric silsesquioxanes with encapsulated fluoride – enhancing reactivity of T8-f poss for materials synthesis. N J Chem 45(9):4227–423510.1039/D0NJ06008A ↗
86. Villaescusa LA, Lightfoot P, Morris RE (2002) Synthesis and structure of fluoride-containing GeO2 analogues of zeolite double four-ring building units. Chem Commun (19):2220–222110.1039/b207374a ↗
87. Villaescusa LA, Wheatley PS, Morris RE, Lightfoot P (2004) A severely interrupted germanate zeolite framework synthesised from isolated double four-ring units. Dalton Trans (5):820–82410.1039/b314942k ↗
88. Sato N, Hayashi T, Tochigi K, Wada H, Shimojima A, Kuroda K (2019) Synthesis of organosilyl-functionalized cage-type germanoxanes containing fluoride ions. Chem Eur J 25(33):7860–786510.1002/chem.201900439 ↗
89. Hayashi T, Sato N, Wada H, Shimojima A, Kuroda K (2021) Variation of counter quaternary ammonium cations of anionic cage germanoxanes as building blocks of nanoporous materials. Dalton Trans 50(24):8497–850510.1039/D1DT01122G ↗
90. Hayashi T, Murase N, Sato N, Fujino K, Sugimura N, Wada H, Kuroda K, Shimojima A (2022) Fluoride ion-encapsulated germoxane cages modified with organosiloxane chains as anionic components of ionic liquids. Organometallics 41(11):1454–146310.1021/acs.organomet.2c00174 ↗
91. Hayashi T, Matsuno T, Kuroda K, Shimojima A (2024) Utilization of cage germoxanes as templates for tuning pore characteristics of siloxane-based materials. Chem Lett 53(3):upae02510.1093/chemle/upae025 ↗
92. Hayashi T, Kuroda K, Shimojima A (2025) Organosilylated cage germoxanes encapsulating fluoride ions for creating functional nanomaterials. Eur J Inorg Chem 28(2):e20240061410.1002/ejic.202400614 ↗
93. Kallus S, Patarin J, Marler B (1996) Synthesis and characterization of a new gallophosphate (Mu-1) containing cobalticinium cations. Microporous Mater 7(2):89–9510.1016/0927-6513(96)00019-3 ↗
94. Kalita AC, Murugavel R (2014) Fluoride ion sensing and caging by a preformed molecular D4R zinc phosphate heterocubane. Inorg Chem 53(7):3345–335310.1021/ic500193n ↗
95. Gupta SK, Kalita AC, Dar AA, Sen S, Patwari GN, Murugavel R (2017) Elusive double-eight-ring zeolitic secondary building unit. J Am Chem Soc 139(1):59–6210.1021/jacs.6b11156 ↗
96. Borah A, Saha J, Sharma S, Chaudhary S, Gupta SK, Rajaraman G, Subramaniam C, Murugavel R (2023) Ligand-field directed electronic effects in heterogenized bifunctional Co(II) molecular clusters accomplish efficient overall water splitting. ACS Catal 13(13):8535–855010.1021/acscatal.2c05942 ↗
97. Eliášová P, Opanasenko M, Wheatley PS, Shamzhy M, Mazur M, Nachtigall P, Roth WJ, Morris RE, Čejka J (2015) The ADOR mechanism for the synthesis of new zeolites. Chem Soc Rev 44(20):7177–720610.1039/C5CS00045A ↗
98. Oh M-H, Kim Y-H, Lee S-M, Hwang G-S, Kim K-S, Kim Y-N, Bae J-Y, Kim J-Y, Lee J-Y, Kim Y-C, Kim SY, Kang S-K (2023) Lifetime-configurable soft robots via photodegradable silicone elastomer composites. Sci Adv 9(34):eadh996210.1126/sciadv.adh9962 ↗
99. Tretbar C, Castro J, Yokoyama K, Guan Z (2023) Fluoride-catalyzed siloxane exchange as a robust dynamic chemistry for high-performance vitrimers. Adv Mater 35(28):230328010.1002/adma.202303280 ↗
100. Debsharma T, Amfilochiou V, Wróblewska AA, De Baere I, Van Paepegem W, Du Prez FE (2022) Fast dynamic siloxane exchange mechanism for reshapable vitrimer composites. J Am Chem Soc 144(27):12280–1228910.1021/jacs.2c03518 ↗