新型铝-硼二吡咯二元化合物：通过光诱导能量转移实现有趣的双发射。
Novel aluminum-BODIPY dyads: intriguing dual-emission via photoinduced energy transfer.
作者信息
Sohn Changho, Jeong Jisu, Lee Ji Hye, Choi Byung Hoon, Hwang Hyonseok, Bae Gyun-Tack, Lee Kang Mun, Park Myung Hwan
机构信息
Department of Chemistry, Institute for Molecular Science and Fusion Technology, Kangwon National University, Chuncheon, Gangwon 24341, Republic of Korea.
出版信息
Dalton Trans. 2016 Apr 7;45(13):5825-32. doi: 10.1039/c5dt05067g. Epub 2016 Mar 3.
Three novel BODIPY-based heterodinuclear complexes, [salen(3,5-(t)Bu)2Al-(OC6H4-BODIPY)] (6), [salen(3,5-(t)Bu)2Al-(OC6F2H2-BODIPY)] (7), and [(mq)2Al-(OC6H4-BODIPY)] (8) (salen = N,N'-bis(salicylidene)ethylenediamine, BODIPY = 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene, and mq = methyl-8-quinolinolato) were prepared and characterized by multinuclear NMR spectroscopy. The specific structures of 6-8 were also determined by single crystal X-ray analysis. In particular, the salen-based heterodinuclear complexes 6 and 7 exhibited higher thermal stability (Td5 = 309 and 306 °C, respectively) than that of the closely related mononuclear aluminum or BODIPY compounds, except for 8. The UV/vis absorption and PL spectra for 6 and 7 indicated a significant photoinduced energy transfer from the aluminum-salen moiety to the BODIPY group in an intramolecular manner. Theoretical calculations revealed independent transition states of the aluminum-salen moiety or the BODIPY group in the Al(III)-BODIPY dyads, further supporting these experimental results.
制备了三种新型基于BODIPY的异双核配合物，[salen(3,5-(t)Bu)2Al-(OC6H4-BODIPY)] (6)、[salen(3,5-(t)Bu)2Al-(OC6F2H2-BODIPY)] (7) 和 [(mq)2Al-(OC6H4-BODIPY)] (8)（salen = N,N'-双（水杨醛）乙二胺，BODIPY = 4,4-二氟-4-硼-3a,4a-二氮杂-s-茚并芴，mq = 甲基-8-喹啉醇），并通过多核核磁共振光谱进行了表征。6-8的具体结构也通过单晶X射线分析确定。特别是，基于salen的异双核配合物6和7表现出比密切相关的单核铝或BODIPY化合物更高的热稳定性（Td5分别为309和306°C），8除外。6和7的紫外/可见吸收光谱和荧光光谱表明在分子内存在从铝-salen部分到BODIPY基团的显著光诱导能量转移。理论计算揭示了Al(III)-BODIPY二元体系中铝-salen部分或BODIPY基团的独立过渡态，进一步支持了这些实验结果。
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