Sohn Changho, Jeong Jisu, Lee Ji Hye, Choi Byung Hoon, Hwang Hyonseok, Bae Gyun-Tack, Lee Kang Mun, Park Myung Hwan
Department of Chemistry, Institute for Molecular Science and Fusion Technology, Kangwon National University, Chuncheon, Gangwon 24341, Republic of Korea.
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。
