Wu Yi Yang, Meng Miao, Wang Gang Yi, Feng Pengju, Liu Chun Y
Department of Chemistry, Jinan University, 601 Huang-Pu Avenue West, Guangzhou 510632, China.
Chem Commun (Camb). 2017 Mar 9;53(21):3030-3033. doi: 10.1039/c7cc00119c.
Four thienylene (CHS) bridged Mo dimers, Mo(DAniF) (DAniF = N,N'-di(p-anisyl)formamidinate), Mo(DAniF), Mo(DAniF) and Mo(DAniF), have been synthesized and studied in terms of electronic coupling. The subtle structural differences between these compounds vary largely the extent of electron delocalization; consequently, a systematic transition from Class II to Class III via Class II-III is achieved, which is probed using spectral parameters of intervalence charge transfer (IVCT) absorption (band energy, intensity and shape) for the mixed-valence complexes. Significantly, the species in Class II-III displays a low energy, half cut-off and solvent-dependent IVCT band, while a high energy, less asymmetrical IVCT band is observed for the complex in Class III. These results give fresh and detailed understanding of the system transition.
合成了四个噻吩撑（CHS）桥联的钼二聚体，即[Mo(DAniF)](μ - OOCCHSCOO)（DAniF = N,N'-二（对甲氧基苯基）甲脒）、[Mo(DAniF)](μ - N(H)SCCHSCN(H)S)、[Mo(DAniF)](μ - OSCCHSCSO)和[Mo(DAniF)](μ - SSCCHSCSS)，并对其电子耦合进行了研究。这些化合物之间细微的结构差异在很大程度上改变了电子离域的程度；因此，实现了从II类到III类经由II - III类的系统转变，这是通过使用混合价配合物的价间电荷转移（IVCT）吸收的光谱参数（带能、强度和形状）来探究的。值得注意的是，II - III类的物种显示出低能量、半截止且依赖溶剂的IVCT带，而III类的配合物观察到高能量、不太不对称的IVCT带。这些结果为系统转变提供了新的详细理解。
