Photochromic hybrid containing in situ-generated benzyl viologen and novel trinuclear [Bi3Cl14]5-: improved photoresponsive behavior by the π···π interactions and size effect of inorganic oligomer.
Two new member of (V)((2n+2)/2)[Bi(2n)Cl(8n+2)] series hybrids, (BzV)2[Bi2Cl10] (1) and (BzV)5[Bi3Cl14]2·(C6H5CH2)2O (2) (where BzV(2+) = N,N'-dibenzyl-4,4'-bipyridinium and (C6H5CH2)2O = dibenzyl ether) have been obtained, and compound 2 contains an unprecedented discrete trimer [Bi3Cl14](5-) counterion. The novel in situ-synthesized symmetric viologen cation with aromatic groups on both sides of 4,4'-bipy would provide more opportunities to create π···π interactions to optimize the photochromic property of the hybrid, and different bismuthated-halide oligomers enable us to discuss the size effect in this series of compounds. Both 1 and 2 are photochromic, and their photoresponsive rate is faster than that of reported viologen-metal halide hybrids. Experimental and theoretical data illustrated that the size of the inorganic oligomer can significantly influence the photoresponsive rate of the viologen dication, and the π···π interaction behaves as not only a powerful factor to stabilize the viologen monocation radical but also the second electron-transfer pathway, from a π-conjugated substituent to a viologen cation, for the photochromic process.
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences , Fuzhou, Fujian 350002, People's Republic of China.
Rong-Guang
RG
Lin
Gang
G
Xu
Gang
G
Lu
Ming-Sheng
MS
Wang
Pei-Xin
PX
Li
Guo-Cong
GC
Guo
D001594:Benzyl Viologen / Q000737:chemistry*; D001729:Bismuth; D002712:Chlorides; D004583:Electrons; D006860:Hydrogen Bonding; D008958:Models, Molecular; D015394:Molecular Structure; D060172:Morpholinos; D009942:Organometallic Compounds / Q000737:chemistry; D055668:Photochemical Processes
D002712:Chlorides; D060172:Morpholinos; D009942:Organometallic Compounds; D001594:Benzyl Viologen; D001729:Bismuth