Borazine-based inorganic–organic hybrid cyclomatrix microspheres by silicon/boron exchange precipitation polycondensation

Riensch, Nicolas A.; Deniz, Ayse; Kühl, Sebastian; Müller, Lars; Adams, Alina; Pich, Andrij; Helten, Holger

doi:10.1039/c7py01006k

Cited by 37 publications

(21 citation statements)

References 55 publications

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“…In an attempt to prepare an essentially linear PIB, we reacted diaminoborane 1 with dichloro‐ n ‐octylborane ( 2 a ; Scheme ). Based on our previous experience with N ‐silylamines combined with chloro‐ or bromoboranes, we anticipated that 1 and 2 a should undergo spontaneous Si/B exchange in solution with elimination of Me 3 SiCl, and the formation of a new B−N bond to give linear diborazene 3 in the first step. Because this species comprises a linear chain of four alternating B and N atoms, unwanted follow‐up reactions to yield small cyclic species should be less likely.…”

Section: Resultsmentioning

confidence: 99%

Cyclolinear Oligo‐ and Poly(iminoborane)s: The Missing Link in Inorganic Main‐Group Macromolecular Chemistry

Ayhan

Riensch

Glasmacher

et al. 2018

Chemistry A European J

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The reaction of n-C H B[N(Me)SiMe ] (1) with n-C H BCl (2 a) yielded, instead of a linear poly(iminoborane), the aminoborane n-C H B(Cl)N(Me)SiMe (4) and after cyclotrimerization the borazine cyclo-(n-C H BNMe) (6). Side reactions that result in borazine formation were effectively suppressed if 1,3-bis(trimethylsilyl)-1,3,2-diazaborolidines 7 were employed as co-monomers in combination with dichloro- or dibromoboranes 2 or 8, respectively. Silicon/boron exchange polycondensation led to oligo(iminoborane)s 11 a,b,ac,d. Alternative synthetic routes to such species involve Sn/B exchange of 1,3-bis(trimethylstannyl)-2-n-octyl-1,3,2-diazaborolidine (16) and n-C H BBr (8 a), and the initiated polycondensation of the dormant monomer 14 in the presence of a Brønsted acid (HCl, HOTf, or HNTf ; Tf=trifluoromethylsulfonyl). Although an attempt to obtain an oligo-/poly(iminoborane) with phenyl side groups yielded only insoluble material, the incorporation of aryl groups was proven for a derivative with both phenyl and n-octyl boron substituents (11 ac), as well as for a derivative with 4-n-butylphenyl side groups (11 d). The highest-molecular-weight sample obtained was 11 ac. Featuring about 18 catenated BN units, on average, this is the closest approach to a poly(iminoborane) known.

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Section: Resultsmentioning

confidence: 99%

Cyclolinear Oligo‐ and Poly(iminoborane)s: The Missing Link in Inorganic Main‐Group Macromolecular Chemistry

Ayhan

Riensch

Glasmacher

et al. 2018

Chemistry A European J

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“…Some of us recently reported a series of BN‐doped inorganic–organic hybrid polymers, including the first poly( p ‐phenylene iminoborane), which can be regarded as a BN‐analogue of poly( p ‐phenylene vinylene) (PPV) . A dapson‐type diaryl sulfone was also incorporated into a polymeric material …”

Section: Methodsmentioning

confidence: 99%

BN‐ and BO‐Doped Inorganic–Organic Hybrid Polymers with Sulfoximine Core Units

Brosge

Lorenz

Helten

et al. 2019

Chemistry A European J

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While polysulfones constitute a class of well‐established, highly valuable applied materials, knowledge about polymers based on the related sulfoximine group is very limited. We have employed functionalized diaryl sulfoximines and a p‐phenylene bisborane as building blocks for unprecedented BN‐ and BO‐doped alternating inorganic–organic hybrid copolymers. While the former were accessed by a facile silicon/boron exchange protocol, the synthesis of polymers with main‐chain B–O linkages was achieved by salt elimination.

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“…In collaborationw ith Pich and co-workers, Helten and coworkers demonstrated the use of Si/B exchange polycondensation also for the synthesis of (nonconjugated) borazine-based hybrid cyclomatrix polymer networks whichf ormed spherical nanoparticles under precipitation polymerization conditions. [56] Lavigne and co-workersp resented evidencef or extended p conjugation also in polymers with BÀOl inkages at trivalent boron. [57] They synthesized poly(dioxaborole) 73 by polycondensation of 9,9-dihexylfluorene-2,7-diboronic acid with 1,2,4,5-tetrahydroxybenzene under Dean-Stark conditions (Scheme 25).…”

Section: Bàecoupling Polymerizationr Outesmentioning

confidence: 96%

“…In collaboration with Pich and co‐workers, Helten and co‐workers demonstrated the use of Si/B exchange polycondensation also for the synthesis of (nonconjugated) borazine‐based hybrid cyclomatrix polymer networks which formed spherical nanoparticles under precipitation polymerization conditions …”

Section: Synthesis Routes To π‐Conjugated Organoborane Polymersmentioning

confidence: 99%

Doping the Backbone of π‐Conjugated Polymers with Tricoordinate Boron: Synthetic Strategies and Emerging Applications

Helten

2019

Chemistry An Asian Journal

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The doping of π‐conjugated organic compounds with trivalent boron atoms produces materials with intriguing properties and functions that result from the interaction of the π‐electron system with the vacant p orbital on boron. This offers unique opportunities in various applications such as organic (opto)electronics, biomedical imaging, and sensors for physiologically relevant anions or amines, as demonstrated by numerous examples on the molecular scale. Recently, the B‐doping strategy has been expanded to polymer chemistry with a view to benefit from the best of both worlds. Herein, recent advances in the synthesis of π‐conjugated polymers doped with tricoordinate boron in the backbone are reviewed. Selected applications are described where these functional materials have already been successfully implemented.

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Borazine-based inorganic–organic hybrid cyclomatrix microspheres by silicon/boron exchange precipitation polycondensation

Abstract: Borazine-based inorganic–organic hybrid cyclomatrix microspheres with a mean diameter of about 900 nm have been obtained via a novel silicon/boron exchange precipitation polycondensation approach.

Cited by 37 publications

References 55 publications

Cyclolinear Oligo‐ and Poly(iminoborane)s: The Missing Link in Inorganic Main‐Group Macromolecular Chemistry

Cyclolinear Oligo‐ and Poly(iminoborane)s: The Missing Link in Inorganic Main‐Group Macromolecular Chemistry

BN‐ and BO‐Doped Inorganic–Organic Hybrid Polymers with Sulfoximine Core Units

Doping the Backbone of π‐Conjugated Polymers with Tricoordinate Boron: Synthetic Strategies and Emerging Applications

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