Photochromic Rh(II) complexes based on 1,2-dicyano-1,2-bis(2,4,5-trimethyl-3-thienyl)ethene
作者:Jing Han、Atsuhiro Nabei、Yusaku Suenaga、Masahiko Maekawa、Hiromichi Isihara、Takayoshi Kuroda-Sowa、Megumu Munakata
DOI:10.1016/j.poly.2006.02.013
日期:2006.9
Reaction of [Rh2(O2CC(CH3)3)4] with cis-1,2-dicyano-1,2-bis(2,4,5-trimethyl-3-thienyl)ethene (cis-dbe) or closed-dbe in benzene and dichloromethane yielded three novel Rh(II) complexes. Their structures were characterized and photochromic properties were studied. X-ray crystallographic analyses revealed that the coordination environments of the three metal complexes are quite different. Complex 2 exhibits
[Rh 2(O 2 CC(CH 3)3)4 ]与顺式-1,2-二氰基-1,2-双(2,4,5-三甲基-3-噻吩基)乙烯(顺式-dbe)的反应或在苯和二氯甲烷中的密闭-dbe生成三种新型Rh(II)配合物。表征了它们的结构并研究了光致变色性质。X射线晶体学分析表明,三种金属配合物的配位环境完全不同。配合物2表现出一维无限链结构,其中配体的两个氰基桥接两个金属离子,而在配合物1和3中所述金属离子与所述两个双噻吩基乙烯分子中的至少一个硫原子具有直接相互作用。在用529nm光激发后,络合物3的闭合dbe在结晶相中转移成开环形式。尽管金属原子与噻吩基配位,但它进行了光环还原反应。不可逆的环化反应大概归因于噻吩基环的固定旋转,较短的RhS距离和阴离子的空间位阻。