Bera Sudip Kumar, Mondal Sudipta, Hazari Arijit Singha, Priego José Luis, Jiménez-Aparicio Reyes, Kaim Wolfgang, Lahiri Goutam Kumar
Department of Chemistry, Indian Institute of Technology Bombay Powai, Mumbai, 400076, India.
Institut für Anorganische Chemie, Universität Stuttgart, Pfaffenwaldring 55, D-70550, Stuttgart, Germany.
Chem Asian J. 2020 Aug 17;15(16):2532-2543. doi: 10.1002/asia.202000326. Epub 2020 Jul 31.
The dianion derived from (2Z,6Z)-3,7-diphenyl-N2,N6-di(pyridin-2-yl)pyrrolo[2,3-f]indole-2,6(1H,5H)-diimine (H BL), a modified BODIPY ligand precursor, is shown to be capable of bridging two metal complex fragments RuL , L=2,4-pentanedionato (acac ), 2,2'-bipyridine (bpy) or 2-phenylazopyridine (pap) in [Ru(acac) Ru(μ-BL)Ru(acac) ] (1/2), Ru(bpy) Ru(μ-BL)Ru(bpy) (3 ) and Ru(pap) Ru(μ-BL)Ru(pap) (4 ). The compounds, including a diastereoisomeric pair 1 (meso) and 2 (rac) were spectroscopically and structurally characterized. Reversible electron transfers as revealed by cyclic and differential pulse voltammetry allowed for an EPR and UV-vis-NIR spectroelectrochemical investigation of several neighboring charge states. Together with susceptibility measurements and TD-DFT calculations the assignment of oxidation states reveals that 1, 2 are diruthenium(III) species which can be oxidized or reduced by one electron whereas 3 and 4 contain ruthenium(II) and get reduced or oxidized mainly at the dianionic bridge (3 ) or are reduced at the ancillary ligands pap (4 ).
由（2Z，6Z）-3,7-二苯基-N2，N6-二（吡啶-2-基）吡咯并[2,3-f]吲哚-2,6（1H，5H）-二亚胺（H BL）衍生的二价阴离子是一种经过修饰的BODIPY配体前体，已证明它能够在[Ru（acac）Ru（μ-BL）Ru（acac）]（1/2）、Ru（bpy）Ru（μ-BL）Ru（bpy）（3 ）和Ru（pap）Ru（μ-BL）Ru（pap）（4 ）中桥连两个金属络合物片段RuL ，其中L = 2,4-戊二酮基（acac ）、2,2'-联吡啶（bpy）或2-苯基偶氮吡啶（pap）。这些化合物，包括非对映异构体对1（内消旋）和2（外消旋），通过光谱和结构进行了表征。循环伏安法和差分脉冲伏安法揭示的可逆电子转移允许对几个相邻电荷态进行电子顺磁共振（EPR）和紫外-可见-近红外光谱电化学研究。结合磁化率测量和含时密度泛函理论（TD-DFT）计算，氧化态的归属表明1、2是二钌（III）物种，可通过一个电子进行氧化或还原，而3和4含有钌（II），主要在二价阴离子桥（3 ）处被还原或氧化，或者在辅助配体pap（4 ）处被还原。
