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Review
. 2023 Dec 15;4(1):7-33.
doi: 10.1021/acspolymersau.3c00030. eCollection 2024 Feb 14.

Carborane-Containing Polymers: Synthesis, Properties, and Applications

Xinyi Zhang  1 , Louis M Rendina  1   2 , Markus Müllner  3   2
Affiliations
Review

Carborane-Containing Polymers: Synthesis, Properties, and Applications

Xinyi Zhang et al. ACS Polym Au. .

Abstract

Carboranes are an important class of electron-delocalized icosahedral carbon-boron clusters with unique physical and chemical properties, which can offer various functions to polymers including enhanced heat-resistance, tuned electronic properties and hydrophobicity, special ability of dihydrogen bond formation, and thermal neutron capture. Carborane-containing polymers have been synthesized mainly by means of step-growth polymerizations of disubstituted carborane monomers, with chain-growth polymerizations of monosubstituted carborane monomers including ATRP, RAFT, and ROMP only utilized recently. Carborane-containing polymers may find application as harsh-environment resistant materials, ceramic precursors, fluorescent materials with tuned emissive properties, novel optoelectronic devices, potential BNCT agents, and drug carriers with low cytotoxicity. This review highlights carborane-containing polymer synthesis strategies and potential applications, showcasing the versatile properties and possibilities that this unique family of boron compounds can provide to the polymeric systems.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Closo-carborane isomers.
Figure 2
Figure 2
Four types of carborane-containing polymers discussed in this review.
Scheme 1
Scheme 1. Some of the Key Polymerization Reactions Discussed in This Review
Scheme 2
Scheme 2. Divinyl Carborane Monomers and Their Resulting Polymers Prepared by Means of ADMET and RCM
Scheme 3
Scheme 3. Dialkynyl Carborane Monomers and Their Resulting Type I Polymers
Scheme 4
Scheme 4. Di(hydroxyphenyl)-carborane Monomer and Its Resulting Type I Polymers
Scheme 5
Scheme 5. Di(hydroxysilyl)-carborane Monomers and Their Resulting Type I Polymers
Scheme 6
Scheme 6. Di(hydroxyalkyl)-carborane Monomers and Their Resulting Type I Polymers
Scheme 7
Scheme 7. Carborane Diamine Monomers and Their Resulting Type I Polymers
Scheme 8
Scheme 8. Dibromo-carborane Monomers and Their Resulting Type I Polymers
Scheme 9
Scheme 9. Dichloro-carborane Monomers and Their Resulting Type I Polymers
Scheme 10
Scheme 10. Dicarboxyl-carborane Monomers and Their Resulting Type I Polymers
Scheme 11
Scheme 11. Distannyl-, Diazido-, and Diacetyl-Carborane Monomers and Their Resulting Type I Polymers
Scheme 12
Scheme 12. Nucleophilic Polycondensation (via Dilithio Intermediate) of closo-1,7-Carborane
Scheme 13
Scheme 13. Sonogashira Polycondensation of a Diiodo-benzocarborane
Scheme 14
Scheme 14. Polythiophene-based Carborane Polymers Obtained via Stille Polycondensation
Scheme 15
Scheme 15. Nucleophilic Polycondensation (Dilithio Intermediate) of closo-1,7-Carborane
Scheme 16
Scheme 16. RAFT Polymerization of Vinyl Carborane Monomers Used to Obtain Type II Polymers
Scheme 17
Scheme 17. ATRP of a Vinyl Carborane Monomer Used to Obtain a Type II Polymer
Scheme 18
Scheme 18. ROP of Cyclic Carborane Monomers Used to Obtain Type II Polymers
Scheme 19
Scheme 19. Other Chain-Growth Polymerizations Used to Obtain Type II Carborane Polymers
Scheme 20
Scheme 20. Type III Polymer Obtained from a Carborane Curing Agent
Scheme 21
Scheme 21. Type III Polymers Obtained from Carborane CTAs
Scheme 22
Scheme 22. Type III Polymers Obtained from Carborane ATRP Initiators
Scheme 23
Scheme 23. Syntheses of Type IV Carborane-Modified Resins
Scheme 24
Scheme 24. Syntheses of Type IV Carborane-Modified Si-based Polymeric Networks
Scheme 25
Scheme 25. Other Type IV Carborane-Containing Polymer Networks and Their Synthesis Methods
Scheme 26
Scheme 26. A Non-network Type IV Polymer Obtained from Carborane ATRP Initiators I3 and I4
Scheme 27
Scheme 27. B10H14-Alkynyl closo-1,2-Carborane Cage-Generating Reaction
Scheme 28
Scheme 28. Nido-carborane-Appended Polymers Generated from closo-1,2-Carborane Polymers by Means of a Regioselective Deboronation Reaction
Scheme 29
Scheme 29. “Click” Reactions Used to Attach Carborane Cages to Polymers
Scheme 30
Scheme 30. Hydrosilylation Reaction Used to Attach Carborane Cages to Polymers
Scheme 31
Scheme 31. Esterification Reaction Used to Attach Carborane Cages to Polymers
Scheme 32
Scheme 32. Host–Guest Interaction Used to Generate Carborane-Containing Polymer Networks
Scheme 33
Scheme 33. Structures of Some Thermo-oxidation Resistant Carborane Polymers
Figure 3
Figure 3
DFT calculations of trimer structures and HOMO/LUMO distributions of I-37–I-39. Reprinted with permission from Filip Aniés et al. Copyright © 2022 Elsevier.
Figure 4
Figure 4
UV–vis absorption spectra of the closo-carborane polymers II-3–II-8 in dilute chlorobenzene solution. Reprinted with permission under a Creative Commons Attribution 3.0 Unported License from Jonathan Marshall et al. Copyright © 2014 Royal Society of Chemistry.
Figure 5
Figure 5
TEM image of carborane self-assemblies of II-12 in water. (A) mPEG44-b-PMPCB6, (B) mPEG113-b-PMPCB3, and (C) mPEG113-b-PMPCB10. Reprinted with permission from Hejian Xiong et al. Copyright © 2016 American Chemical Society.
See this image and copyright information in PMC

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