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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >On the ambiguity of 1,3,2-benzodiazaboroles as donor/acceptor functionalities in luminescent molecules
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On the ambiguity of 1,3,2-benzodiazaboroles as donor/acceptor functionalities in luminescent molecules

机译：关于1,3,2-苯并二氮杂硼烷在发光分子中作为供体/受体功能的歧义

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摘要

A series of 1,3-bis(perfluoroaryl)-2-(hetero)aryl-1,3,2-benzodiazaboroles, 1,3-~FAr_2-2-Ar-1,3,2-N_2BC_6H_4 (Ar = Ph, ~FAr = C_6F_5 5; Ar = Ph, ~FAr = 4-C_5F_4N 6; Ar = Ph, ~FAr = 4-NCC_6F_4 7; Ar = 2-C_4H_3S, ~FAr = C_6F_5 8; Ar = 2-C_4H_3S, ~FAr = 4-C_5F_4N 9; Ar = 2-C_4H_3S, ~FAr = 4-NCC_6F_4 10), were synthesised by cyclocondensa- tion of the adducts PhBBr_2·PPh_3 or 2-thienylBBr_2·PPh_3 with N,N'-bis(perfluoroaryl)-o-phenylenediamines in the presence of 2,2,6,6-tetramethylpiperidine. Similar treatments of the PPh_3 adducts of 4-(1',3'- diethyl-1',3',2'-benzodiazaborolyl)-phenyldibromoborane with the corresponding diamines gave rise to the push-pull compounds, C_6H_4(NEt)_2B-1,4-C_6H_4-B(N~FAr)_2C_6H_4 (~FAr = C_6F_5 11; 4-C_5F_4N 12) and C_6H_4(NEt)_2B-2,5-C_4H_2S-B(N~FAr)_2C_6H_4 (~FAr = C_6F_5 13; 4-C_5F_4N 14). The X-ray structures of 8, 11, 12 and 13 were determined. Electronic structure calculations reveal that the LUMOs are located at the perfluoro- aryl groups in 5-14; thus the fluorinated benzodiazaborolyl groups are considered as electron-withdraw- ing moieties. These moieties differ from alkylated benzodiazaborolyl groups which are regarded as donors. The emission spectra for 5-14 show charge transfer bands with signi?cant solvatochromism and large Stokes shifts (6100-12 500 cm~(?1) in cyclohexane and 8900-15 900 cm~(?1) in CH_2Cl_2). The emissions of the benzodiazaboroles, 5-10, arise from a different charge transfer (CT) process to the local charge transfer (LCT) process typically found in many fluorescent benzodiazaboroles. This novel remote charge transfer (RCT) process involving the perfluoroaryl groups is supported by CAM-B3LYP computations. The push-pull systems 11-14 here give fluorescent emissions with moderate to high fluorescence quantum yields (65-97%) that arise from the usual LCT process only.
机译：一系列1,3-双（全氟芳基）-2-（杂）芳基-1,3,2-苯并二氮杂硼烷，1,3-〜FAr_2-2-Ar-1,3,2-N_2BC_6H_4（Ar = Ph， 〜FAr = C_6F_5 5; Ar = Ph，〜FAr = 4-C_5F_4N 6; Ar = Ph，〜FAr = 4-NCC_6F_4 7; Ar = 2-C_4H_3S，〜FAr = C_6F_5 8; Ar = 2-C_4H_3S，〜FAr = 4-C_5F_4N 9; Ar = 2-C_4H_3S，〜FAr = 4-NCC_6F_4 10）是通过加成物PhBBr_2·PPh_3或2-噻吩基BBr_2·PPh_3与N，N'-双（全氟芳基）-在2,2,6,6-四甲基哌啶存在下的邻苯二胺。 4-（1'，3'-二乙基-1'，3'，2'-苯并二氮杂硼烯丙基）-苯基二溴硼烷的PPh_3加合物与相应的二胺的相似处理产生推挽化合物C_6H_4（NEt）_2B- 1,4-C_6H_4-B（N〜FAr）_2C_6H_4（〜FAr = C_6F_5 11; 4-C_5F_4N 12）和C_6H_4（NEt）_2B-2,5-C_4H_2S-B（N〜FAr）_2C_6H_4（〜FAr = C_6F_5 13; 4-C_5F_4N 14）。确定了8、11、12和13的X射线结构。电子结构计算表明，LUMOs位于5-14的全氟芳基上。因此，氟化苯二氮杂硼烯丙基被认为是吸电子部分。这些部分不同于被认为是供体的烷基化苯并二氮杂硼烷基。 5-14的发射光谱显示出具有显着的溶剂变色和大斯托克斯位移的电荷转移带（在环己烷中为6100-12 500 cm〜（？1），在CH_2Cl_2中为8900-15 900 cm〜（？1））。 5-10苯并二氮杂硼烷的发射源于通常在许多荧光苯并二氮杂硼酸酯中发现的局部电荷转移（CT）过程与局部电荷转移（LCT）过程不同。 CAM-B3LYP计算支持这种涉及全氟芳基的新型远程电荷转移（RCT）过程。这里的推挽系统11-14产生的荧光发射具有中等到较高的荧光量子产率（65-97％），这仅是通过普通LCT过程产生的。

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