Xu Guang-Tao, Li Bin, Wang Jin-Yun, Zhang Dao-Bin, Chen Zhong-Ning
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 155 Yangqiao Road West, Fuzhou, Fujian 350002 (P.R. China).
Chemistry. 2015 Feb 16;21(8):3318-26. doi: 10.1002/chem.201405464. Epub 2015 Jan 9.
Heteronuclear complexes FeCp2 -DTE-C≡C-Ru(dppe)2 Cl (1 o; dppe=1,2-bis(diphenylphosphino)ethane, Cp=cyclopentadienyl, DTE=dithienylethene) and FeCp2-DTE-C≡C-Ru(dppe)2-C≡C-DTE-FeCp2 (2 oo), with redox-active ferrocenyl and ruthenium centers separated by a photochromic DTE moiety, were prepared to achieve photoswitchable charge delocalization and Fe⋅⋅⋅Ru electronic communication. Upon UV-light irradiation of 2 oo, the Fe⋅⋅⋅Ru heterometallic electronic interaction is increasingly facilitated with stepwise photocyclization, 2 oo→2 co→2 cc; this is ascribed to the gradual increase in π-conjugated systems. The near-infrared absorptions in mixed-valence species 2 oo /2 co /2 cc are gradually intensified following the conversion of 2 oo →2 co →2 cc , which demonstrates that the extent of charge delocalization shows progressive enhancement with stepwise photocyclization. As revealed by electrochemical, spectroscopic, and theoretical studies, complex 2 exhibits nine switchable states through stepwise photochromic and reversible redox processes.
制备了异核配合物二茂铁二噻吩乙烯乙炔钌二（二苯基膦基）乙烷（1 o；二苯基膦基乙烷=dppe，环戊二烯基=Cp，二噻吩乙烯=DTE）和二茂铁二噻吩乙烯乙炔钌二（二苯基膦基）乙炔二噻吩乙烯二茂铁（2 oo），其氧化还原活性的二茂铁基和钌中心被光致变色的DTE部分隔开，以实现光开关电荷离域和铁⋅⋅⋅钌电子通讯。对2 oo进行紫外光照射时，随着逐步光环化2 oo→2 co→2 cc，铁⋅⋅⋅钌异金属电子相互作用越来越容易发生；这归因于π共轭体系的逐渐增加。混合价态物种2 oo /2 co /2 cc中的近红外吸收随着2 oo →2 co →2 cc的转变而逐渐增强，这表明电荷离域程度随着逐步光环化而逐渐增强。电化学、光谱和理论研究表明，配合物2通过逐步光致变色和可逆氧化还原过程呈现出九种可切换状态。
