Electron-deficient viologens are widely used as ligands or structure-directing agents(SDAs)to synthesize crystalline X-ray induced photochromic materials.Here,a new rational strategy of anion-directed fold-ing a flexi...Electron-deficient viologens are widely used as ligands or structure-directing agents(SDAs)to synthesize crystalline X-ray induced photochromic materials.Here,a new rational strategy of anion-directed fold-ing a flexible cation(H_(2)imb)^(2+)((H_(2)imb)^(2+)=di-protonated 2,3-bis(imidazolin-2-yl)-2,3-dimethylbutane)has been developed.Electron-donating Cl−and(ZnCl4)2−are used to direct folding a flexible electron-deficient(H_(2)imb)^(2+)cation.Three complexes(H_(2)imb)(NO_(3))2(1),(H_(2)imb)Cl2·H_(2)O(2),and(H_(2)imb)ZnCl4(3)have been synthesized in which(H_(2)imb)^(2+)crystallize in an anti-conformation,88.8°-gauche,and 51.8°-gauche,respectively.In contrary to X-ray silent complex 1,X-ray induced photochromism has been achieved in both complex 2 and 3.An intermolecular charge-transfer mechanism has been elucidated and the anion directed folding of(H_(2)imb)^(2+)has been validated to be critical to yield colored long-lived charge-separated states.展开更多
Most porous conductive frameworks are highly anisotropic in their structures thus leading to anisotropic charge transport.Here we report a supramolecular self-assembly which is constructed by intermolecular hydrogen b...Most porous conductive frameworks are highly anisotropic in their structures thus leading to anisotropic charge transport.Here we report a supramolecular self-assembly which is constructed by intermolecular hydrogen bonding andπ···πinteractions.This material features a chiral,porous,cubic framework structure withπ-stacked helical columns along all of the three Cartesian coordinates.As a result,isotropic charge transport with an electrical conductivity(σ)of 2.1×10^(–7)S/cm is achieved.By achieving isotropic charge transport in aπ-stacked supramolecular assembly,these results provide a new type of isotropic conductive framework materials alternative to conductive metal-organic frameworks(MOFs).展开更多
基金supported by National Natural Science Foundation of China(No.92261109)Natural Science Foundation of Fujian Province(No.2020J05080)+3 种基金Project Funded by China Postdoctoral Science Foundation(No.2023M733496)Natural Science Foundation of Xiamen(No.3502Z20206080)Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(No.2021ZR110)Recruitment Program of Global Youth Experts,Youth Innovation Promotion Association CAS(No.2021302).
文摘Electron-deficient viologens are widely used as ligands or structure-directing agents(SDAs)to synthesize crystalline X-ray induced photochromic materials.Here,a new rational strategy of anion-directed fold-ing a flexible cation(H_(2)imb)^(2+)((H_(2)imb)^(2+)=di-protonated 2,3-bis(imidazolin-2-yl)-2,3-dimethylbutane)has been developed.Electron-donating Cl−and(ZnCl4)2−are used to direct folding a flexible electron-deficient(H_(2)imb)^(2+)cation.Three complexes(H_(2)imb)(NO_(3))2(1),(H_(2)imb)Cl2·H_(2)O(2),and(H_(2)imb)ZnCl4(3)have been synthesized in which(H_(2)imb)^(2+)crystallize in an anti-conformation,88.8°-gauche,and 51.8°-gauche,respectively.In contrary to X-ray silent complex 1,X-ray induced photochromism has been achieved in both complex 2 and 3.An intermolecular charge-transfer mechanism has been elucidated and the anion directed folding of(H_(2)imb)^(2+)has been validated to be critical to yield colored long-lived charge-separated states.
基金supported by the National Natural Science Foundation of China(Nos.21871262 and 21901242)the Natural Science Foundation of Fujian Province(No.2020J05080)+3 种基金the Natural Science Foundation of Xiamen(No.3502Z20206080)Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(No.2021ZR110)the Recruitment Program of Global Youth ExpertsYouth Innovation Promotion Association CAS(No.2021302)。
文摘Most porous conductive frameworks are highly anisotropic in their structures thus leading to anisotropic charge transport.Here we report a supramolecular self-assembly which is constructed by intermolecular hydrogen bonding andπ···πinteractions.This material features a chiral,porous,cubic framework structure withπ-stacked helical columns along all of the three Cartesian coordinates.As a result,isotropic charge transport with an electrical conductivity(σ)of 2.1×10^(–7)S/cm is achieved.By achieving isotropic charge transport in aπ-stacked supramolecular assembly,these results provide a new type of isotropic conductive framework materials alternative to conductive metal-organic frameworks(MOFs).
