摘要
Aldehyde groups were intentionally equipped on the cyanide-bridged[Fe_(2)Co_(2)]square molecules:{[(Tp*)Fe(CN)_(3)Co(bpy^(CHO))_(2)]_(2)-[PF_(6)]_(2)}·4MeOH(1,Tp*=hydrotris(3,5-dimethylpyrazol-1-yl)borate;bpy^(CHO)=4-formyl-4′-methyl-2,2′-bipyridine),thus providing chemical-active windows for post-modification towards desired functions.In this contribution,by taking advantage of efficient Schiff-base condensation between the aldehyde-substituted bipyridine derivative(bpyCHO)and alkyl diamines(H_(2)N-(CH_(2))_(n)NH_(2)),two discrete[Fe_(2)Co_(2)]compounds{[(Tp∗)Fe(CN)_(3)Co(bpy^(C=N(CH_(2))_(n)N=C)bpy)]2[PF_(6)]_(2)}⋅6DMF(2,n=5;3,n=7)were prepared,where the cyanide-bridged[Fe_(2)Co_(2)]square cores were encapsulated by the flexible alkyl chains.Variable-temperature single-crystal X-ray diffraction and magnetic studies revealed complete thermo(T_(1/2)=233 K(2)and 237 K(3))and photo-induced electron transfer event accompanying spin transition between the diamagnetic[Fe^(Ⅱ)_(LS2)Co^(Ⅲ)_(LS2)]state and the paramagnetic[Fe^(Ⅲ)_(LS2)Co^(Ⅱ)_(HS2)]state(LS,low spin;HS,high spin).In addition,the bidirectional switching between the two states was achieved with alternating laser irradiation at 808 and 532 nm at 10 K.
基金
This work was supported by the National Natural Science Foundation of China(21671095,21901108),and start-up fund from SUSTech.We thank Dr.Bin Chen from Soochow University for UV-Vis-NIR measurements.
