The synthesis of a highly twisted chrysene derivative incorporating two electron deficient o‐carboranyl groups is reported. The molecule exhibits a complex, excitation‐dependent photoluminescence, including aggregation‐induced emission (AIE) with good quantum efficiency and an exceptionally long singlet excited state lifetime. Through a combination of detailed optical studies and theoretical calculations, the excited state species are identified, including an unusual excimer induced by the presence of o‐carborane. This is the first time that o‐carborane has been shown to induce excimer formation ab initio, as well as the first observation of excimer emission by a chrysene‐based small molecule in solution. Bis‐o‐carboranyl chrysene is thus an initial member of a new family of o‐carboranyl phenacenes exhibiting a novel architecture for highly‐efficient multi‐luminescent fluorophores.
Rhodium(II) catalysts and PhIO in benzene convert homoallylic carbamates into the corresponding aziridines at room temperature.
The synthesis of ahighly twisted chrysenederivative incorporating two electron deficient o-carboranyl groups is reported. The molecule exhibits ac omplex, excitation-dependent photoluminescence,i ncluding aggregation-induced emission (AIE) with good quantum efficiency and an exceptionally long singlet excited state lifetime.T hrough ac ombination of detailed optical studies and theoretical calculations,the excited state species are identified, including an unusual excimer induced by the presence of o-carborane.T his is the first time that o-carborane has been shown to induce excimer formation ab initio,aswell as the first observation of excimer emission by achrysene-based small molecule in solution. Bis-o-carboranyl chrysene is thus an initial member of an ew family of ocarboranyl phenacenes exhibiting an ovel architecture for highly-efficient multi-luminescent fluorophores.Atfirst glance,b ulky boron-rich spheroids appear to be an anathema to the two-dimensional, p-conjugated world of organic electronics.O nt he contrary,m otivated by their unique three-dimensional s-delocalization, electron-withdrawing ability (when substituted at the carbon vertices), [1] and high thermal and chemical stability,c arboranes,a nd principally o-carborane (C 2 B 10 H 12 ), have now been incorporated in aw ide range of molecular and polymeric semiconductors. Ak ey property of o-carborane is its ability to accept an excited charge via intramolecular charge transfer (ICT) from an aryl donor group,o ccurring most efficiently when the carborane has its C À Cb ond perpendicular to the aromatic plane.T hese ICT states are notable for their flexible carboranyl CÀCb ond, which can vibrate and relax nonradiatively,o rr adiatively with ah ighly red-shifted emission. [24][25][26][27][28][29][30] Such systems often exhibit aggregation-induced emission (AIE), [13-15,17-20, 22, 31, 32] that is,i na na ggregated state where molecular motion is restricted, non-radiative relaxation pathways from the ICT state are inhibited, leading to as ignificant increase in emission efficiency. It has been demonstrated that incorporation of bulky carboranes on the long edges of linear acenes creates al arge steric hinderance between the carboranes and proximal protons,l eading to aconsiderable deformation of the ring system. [15][16][17] With this comes alarge increase in the carborane rotation barrier, and generally am ore rigid structure;aproperty known to be useful for AIE.o-Carborane has also been shown, to av ery limited extent, to aid excimer emission. When di-substituted with two naphthyl donor groups,t he imposed proximity of the aryl systems allows for an overlap of the aromatic wavefunctions, such that dimerization occurs readily when one naphthalene is in the excited state.[27] In other cases where o-carborane has been attached to pyrene,t he bulky carborane moiety was found not to inhibit the p-p stacking required for pyrene excimer formation. [19,20,23] In these few cases,h owever, the carborane can be considered essentially electronica...
We present the novel 1,4-difunctionalisation of benzocarborane with organometallic groups suitable for cross-coupling and its subsequent insertion for the first time into conjugated polymer backbones. Copolymers with solubilised cyclopentadithiophene and diketopyrrolopyrrole derivatives were prepared by Stille polymerisation in good molecular weight. The physical, material and optoelectronic properties of the resulting polymers were investigated, demonstrating that benzocarborane acts similarly to a stabilised, electron-deficient cis-diene linker. We also report the first polymer field effect transistors incorporating a benzocarborane in the backbone.
ReferencesS10 Gaussian Cartesian coordinates S11-S24 S2 Monomer Synthesis Scheme 1. Synthesis of Benzocarborano[2,1-b:3,4-b']dithiophene (BZTT) 2-bromo-3-iodothiophene (A)Following a modified literature procedure, 1 3-iodothiophene (30 g, 143 mmol) was dissolved in glacial acetic acid (300 mL) before N-bromosuccinimide (26.7 g, 150 mmol) was added portionwise with rapid stirring. The resultant mixture was heated to 120˚C for two hours before being allowed to cool to room temperature and poured into cold water (250 mL). The resultant mixture was extracted with diethyl ether and the organic layers were combined, washed with saturated sodium sulphite solution, water and brine before being dried over magnesium sulphate, filtered and concentrated under reduced pressure. Purification by column chromatography (eluent: hexane) afforded the desired product as a colourless oil (31.1 g, 108 mmol, 76%).
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