Photoswitchable electrochemical behaviour of a [FeFe] hydrogenase model with a dithienylethene derivative.
A diiron dithiolate complex 1o with a dithienylethene (DTE) phosphine ligand has been elaborately designed and fully investigated by spectroscopic and DFT computational studies. Upon irradiation with UV light, the DTE moiety in complex 1o undergoes an excellent photocyclization reaction to attain ring-closed state 1c in high yield (>95%), accompanied by a colour change from orange to deep blue. On the other hand, upon irradiation with visible light (>460 nm), ring-closed form 1c in CH(3)CN solution reverts perfectly into ring-open form 1o. Both 1o and 1c were characterised by IR, (1)H, (31)P, (19)F NMR and electrochemical spectroscopy. The electrochemical behaviours of both the open and closed forms were investigated by cyclic voltammetry. Upon photocyclization reaction, a 290 mV (from -2.29 V to -2.00 V) positive shift is induced in the potential of electrochemical catalytic proton reduction, due to the electron-withdrawing effect of the ring-closed DTE moiety. Consequently, complex 1 can reversibly photoswitch the potential of proton reduction on the [FeFe] moiety.
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China.
Hui-Min
HM
Wen
Jin-Yun
JY
Wang
Ming-Qiang
MQ
Hu
Bin
B
Li
Zhong-Ning
ZN
Chen
Chang-Neng
CN
Chen
D056831:Coordination Complexes / Q000737:chemistry; D055664:Electrochemical Techniques; D005290:Ferric Compounds / Q000737:chemistry; D006864:Hydrogenase / Q000737:chemistry* / Q000378:metabolism; D007506:Iron-Sulfur Proteins / Q000737:chemistry* / Q000378:metabolism; D008958:Models, Molecular; D013055:Spectrophotometry, Infrared; D013438:Sulfhydryl Compounds / Q000737:chemistry; D014466:Ultraviolet Rays
D056831:Coordination Complexes; D005290:Ferric Compounds; D007506:Iron-Sulfur Proteins; D013438:Sulfhydryl Compounds; C118830:iron hydrogenase; D006864:Hydrogenase