A series of p‐nido‐carborane‐triarylborane conjugates (nido‐1‐3) in which a methyl group is introduced at the ortho‐position to the carborane cage in the phenylene linker was prepared and characterized. All compounds exhibit broad low‐energy absorptions (λ_abs = ca. 350–400 nm) attributable to the intramolecular charge transfer transition from the nido‐carborane donor to the (MePh)BMes₂ acceptor. Electrochemical studies confirm that oxidation occurs at the nido‐carborane while the boryl moieties are responsible for the reduction. All nido‐compounds show broad green emissions in tetrahydrofuran (THF) with good photoluminescence (PL) quantum yields (Φ_PL = 24%–78%). In particular, different from the almost non‐thermally activated delayed fluorescence (TADF) properties of unsubstituted para‐conjugates, the transient PL decay curves of nido‐1‐3 show the existence of weak TADF (τ_d = 0.9–1.4 μs in THF). The TADF properties are further supported by the very small singlet‐triplet energy splitting below 0.15 eV and are also observed in poly(methyl methacrylate) (PMMA) films doped with nido‐1‐3.

中文翻译：

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对-N-碳硼烷-三芳基硼烷与甲基取代的亚苯基连接物的合成及延迟荧光性质

一系列的对-巢-carborane-三芳基偶联物（巢- 1 - 3），其中甲基是在引入的邻位上的亚苯基连接基碳硼烷笼制备和表征。所有化合物表现出宽的低能量吸收（λ _ABS =约350-400纳米）可归因于从该分子内电荷转移过渡巢-carborane施主到（麦菲）BMES ₂受体。电化学研究证实，氧化反应发生在氨基碳硼烷上，而硼基部分负责还原。所有的尼多-化合物显示在四氢呋喃（THF）具有良好的光致发光（PL）量子产率（宽绿排放Φ _PL = 24％-78％）。具体地讲，从几乎不热活化延迟荧光（TADF）未取代的性质的不同段-conjugates，瞬态PL衰减曲线巢- 1 - 3示出弱TADF的存在（τ _d = 0.9-1.4微秒的THF ）。的TADF性质通过下面0.15电子伏特的非常小的单线态-三线态能量分裂进一步支持和在聚（甲基丙烯酸甲酯）还观察到（PMMA）膜掺杂有巢- 1 - 3。