Luminescent m-Carborane-Based π-Conjugated Polymer

Abstract

A series of m-carborane-based π-conjugated polymers were successfully synthesized via Sonogashira−Hagihara polycondensation reaction. Diiodo-m-carborane monomer underwent efficient polycondensation reaction with both electron-donating and electron-accepting diyne comonomers. The wide-angle structure of m-carborane monomer allowed the preparation of polymers with high molecular weights (M n = 26 600−36 400 g mol−1) and good polymerization degrees (DP = 31−56). UV−vis absorption study in dilute CHCl3 solution revealed π-conjugation extension of a p-phenylene−ethynylene segment by introducing m-carborane moieties into the polymer backbone. Further, the lack of C−C bond in the carborane cluster leads to polymers exhibiting intense blue emission in solution state (ΦF = 0.11−0.26).

C,C′-Bis(benzodiazaborolyl)dicarba-closo-dodecaboranes: Synthesis, structures, photophysics and electrochemistry

“…4,7,[9][10][11][12][13][14][15][16][17][18][19] Due to similarities in their sizes, the para-carborane motif -CB 10 H 10 C-has been compared with the para-phenylene spacer 1,4-C 6 H 4 -in donor-acceptor molecules. There, however, the carborane behaved as an effective insulator, whereas the phenylene-moiety is well known as an electron-conducting conjugated -system.…”

“…Yield: 0.09 g (16 %). Found: C,53.69;H,7.81;N,11.47 %;C 22 H 38 B 12 N 4 requires C,54.11;H,7.84;N,11. …”

“…3 These carboranes have only recently been considered as potential components for OLEDs in photophysical studies on C,C-diarylated dicarbadodecaboranes. [4][5][6][7][8][9][10][11][12][13] Selected photophysical data for some C,C-diarylcarboranes are summarized in Chart 1.…”

Bi-functional Li2B12H12 for energy storage and conversion applications: solid-state electrolyte and luminescent down-conversion dye

“…25 Because of their three dimensional aromaticity, these compounds have the ability to undergo a variety of organic transformations, and extend the π-conjugation of polyaromatic system. [26][27][28][29] This property has led to the use of carboranes as building blocks for solid state emitting materials. [30][31][32] In these systems, the photophysical properties can be fine-tuned by controlling the aggregate induced emission (AIE) and electronic structure of the attached functional groups.…”

Polymer reaction of poly(p-phenylene–ethynylene) by addition of decaborane: modulation of luminescence and heat resistance

“…[18][19][20][21][22][23][24] Recently, we reported the synthesis of novel p-conjugated polymers with an icosahedral carborane cluster in their main chain, their great thermal durability and surprising optical properties, that is, aggregation-induced emission based on the molecular orbital of o-carborane. [25][26][27][28][29][30][31][32] Although the hybridization of p-conjugated polymers with inorganic clusters has given prominent results, the multistep synthesis of monomers containing inorganic clusters would have obstructed a thorough investigation in this field. One methodology to lessen the burden on synthesis is the polymer reaction of p-conjugated polymers.…”