Regulation of Charge Delocalization in a Heteronuclear Fe2Ru System by a Stepwise Photochromic Process |
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| Authors: | Guang‐Tao Xu Dr Bin Li Dr Jin‐Yun Wang Dr Dao‐Bin Zhang Prof Zhong‐Ning Chen |
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| Institution: | 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) |
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| Abstract: | Heteronuclear complexes FeCp2?DTE?C?C?Ru(dppe)2Cl ( 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. |
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| Keywords: | charge transfer metal– metal interactions mixed‐valent compounds photochromism ruthenium |
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