Asymmetric oxidation of vinyl- and ethynyl terthiophene ligands in triruthenium complexes

作者：Zhang, Jing; Sun, Chao-Fang; Zhang, Ming-Xing; Hartl, Frantisek^*; Yin, Jun; Yu, Guang-Ao; Rao, Li; Liu, Sheng Hua

来源：Dalton Transactions, 2016, 45(2): 768-782.

DOI：10.1039/c5dt04083c

• MIXED-VALENCE SYSTEMS
• BIMETALLIC RUTHENIUM COMPLEXES
• INTRAMOLECULAR ELECTRON-TRANSFER
• PHOTOSWITCHABLE MOLECULAR WIRE
• TRANSITION-METAL-COMPLEXES
• CENTRAL PHENYLENE RING
• SOLID-STATE STRUCTURE
• DIRUTHENIUM COMPLEXES
• CHARGE DELOCALIZATION
• DITHIENYLETHENE DTE

A series of ruthenium(II) complexes [{RuCl(CO)(PMe3)(3)(-CH=CH-)}(n)X], 1a-1c (1a: n = 3, X = 3,3 ''-dimethyl- 2,2':3', 2 ''-terthiophene; 1b: n = 2, X = 2,2'-bithiophene; 1c: n = 2, X = 2,3-bis(3-methylthiophen-2-yl)benzothiophene) and [{Cp*(dppe)(2)Ru(-C C-)}(3)X], 1d (X = 3,3 ''-dimethyl-2,2':3',2 ''-terthiophene), were prepared and characterized by H-1, C-13 and P-31 NMR. Their redox, spectroscopic and bonding properties were studied with a range of spectro-electrochemical methods in combination with density functional theory calculations. The first two anodic steps observed for 1a and 1d are largely localized on the lateral frameworks of the molecular triangle, the direct conjugation between them being precluded due to the photostable open form of the dithienyl ethene moiety. The third anodic step is then mainly localized on the centerpiece of the triangular structure, affecting both bithiophene laterals. The experimental IR and UV-vis-NIR spectroelectrochemical data and, largely, also DFT calculations account for this explanation, being further supported by direct comparison with the anodic behavior of reference diruthenium complexes 1b and 1c.

• 出版日期2016
• 单位华中师范大学