α-取代苯并噻吩钌乙炔及钌乙烯配合物的合成、表征、电化学及光谱电化学性质

Syntheses, Characterization, Electrochemistry and Spectroelectrochemistry ofα-Benzothiophene Acetyl and Vinyl Mononuclear Ruthenium Complexes

以α-取代苯并噻吩乙炔及乙烯基为配体,与不同辅助配体键合的金属钌为氧化还原活性端基,分别合成并表征了α-取代苯并噻吩钌乙炔及钌乙烯配合物1和2,两个配合物均经X射线单晶衍射的确证。电化学性质表明配合物1具有较好的氧化还原可逆性,金属氧化态相对于2比较稳定。红外光谱电化学研究表明配合物1和2分别形成1^+和2^+后,与金属相连的ν(C≡C)和ν(C≡O)伸缩振动吸收均发生变化,其中ν(C≡C)变化较大,可能由于形成了Ru=C=C结构;紫外可见近红外光谱电化学研究发现电解后,中性分子1和2在紫外区域的强吸收峰均逐渐降低,1^+分别在可见及近红外580 nm,698 nm及874 nm处出现较弱的3个吸收峰,3个吸收峰可能归属于LMCT吸收。2^+在296 nm处出现1个很弱的吸收峰,这不同于配合物1^+,可能源于2^+的稳定性。

Using α-benzothiophene acetyl and vinyl as ligands, metal Ru with different auxiliary ligands as redox-active terminus, we synthesized and characterized α-benzothiophene substituted mononuclear ruthenium acetyl and vinyl complexes 1 and 2. Two complexes were confirmed by X-ray single crystal diffraction. Electrochemical properties suggest that complex 1 has better redox reversibility, corresponding oxidation state 1^＋is more stable than2^＋; IR Spectroelectrochemical studies found that 1 and 2 are oxidized into respective 1^＋and 2^＋, and respectiveν（C≡C） and ν（C≡O） stretching vibration absorptions both have obvious changes： changes of ν（C≡C） is larger,which may be result from the formation of Ru =C =C; UV-Vis-NIR spectroelectrochemistry shows that after electrolytic, absorptions of neutral 1 and 2 in UV region fall down gradually, and 1^＋displayed three weak absorptions in visible and NIR region（580 nm, 698 nm and 874 nm）, which may be assigned to LMCT contributions. 2^＋is different from 1^＋, which appears only a weak peak at 296 nm, and may be attributable to the stability of 2^＋. CCDC： 1441747, 1; 1443680, 2.