o-Carborane was used to alter the electronic states of π-conjugated organic aryls and was demonstrated as an effective optical and electronic control unit to tune the photophysical properties, endowing the molecules with certain luminescence properties and modifying the HOMO and LUMO energies for electron transfer. We introduced fluorene and its heteroanalogs (carbazole, dibenzofuran and dibenzothiophene), four types of substitutes with different electron-rich or electron-deficient heteroatoms, to the two carbon atoms of o-carborane to synthesize CDC, CDN, CDO and CDSvia a modified nickel-catalyzed cross-coupling reaction. The photophysical properties of o-carborane-containing heterocyclic compounds were investigated and compared with each other. The results showed that all compounds were AIE luminogens with tunable fluorescence colors from blue to yellow emissions (λ_em = 465–570 nm) and possessed excellent emission quantum efficiencies in the solid state (Φ_F > 70%). Among the four o-carborane-containing heterocyclic compounds, the ground state structures confirmed by crystallographic measurements provided a close correlation of the structure and electronic properties between the π-conjugated organic aryl groups and o-carborane. Besides, the heteroatoms controlled and altered the electronic interaction between aryls and o-carborane due to the different electron-rich or electron-deficient attributes. The HOMO and LUMO energies were estimated by DFT calculations. The excited states were calculated by TD-DFT and correlated with the corresponding absorption and emission spectra to systematically elucidate the electronic perturbation. This work not only demonstrates an efficient strategy for constructing o-carborane-containing heterocyclic AIE luminogens but also indicates that they are promising as advanced optoelectronic materials.

中文翻译：

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聚集诱导的邻碳烷官能化芴及其杂类似物的发射特性：杂原子对光致发光的影响

邻-甲硼烷可用于改变π共轭有机芳基的电子状态，并被证明是一种有效的光学和电子控制单元，可调节光物理性质，赋予分子某些发光性质并改变HOMO和LUMO能量以进行电子转移。我们将芴及其杂类似物（咔唑，二苯并呋喃和二苯并噻吩）（具有不同的富电子或缺电子的杂原子的四种类型的取代基）引入到邻碳硼烷的两个碳原子上，以通过改进的方式合成CDC，CDN，CDO和CDS镍催化的交叉偶联反应。o的光物理性质研究并比较了含碳硼烷的杂环化合物。结果表明，所有化合物都AIE luminogens具有可调荧光颜色从蓝色到黄色的排放（λ _EM = 465-570纳米）和具有在固体状态（优异的发射量子效率Φ _˚F > 70％）。在这四种含邻碳硼烷的杂环化合物中，通过晶体学测量证实的基态结构提供了π-共轭有机芳基和邻碳硼烷之间的结构和电子性质的紧密相关性。此外，杂原子控制并改变了芳基与邻位之间的电子相互作用。-碳硼烷由于具有不同的富电子或缺电子特性。通过DFT计算估算HOMO和LUMO能量。激发态通过TD-DFT计算得出，并与相应的吸收和发射光谱相关，以系统地阐明电子扰动。这项工作不仅证明了一种有效的策略，用于构建含邻甲硼烷的杂环AIE发光剂，而且表明它们有望作为先进的光电材料。