By virtue of a 3∶1 complementary coordination strategy,a chiral heteroleptic metal-organic cage that con-tains divergent functional units,Pd‑R(Zn),was precisely constructed via self-assembly of monodentate variationa...By virtue of a 3∶1 complementary coordination strategy,a chiral heteroleptic metal-organic cage that con-tains divergent functional units,Pd‑R(Zn),was precisely constructed via self-assembly of monodentate variational Zn-salen ligands RZn and NADH(reduced nicotinamide adenine dinucleotide)mimic modified tridentate ligands with square-planar Pd ions.UV-Vis and luminescence spectra experiments reveal that different anions could selec-tively interact with different sites of Zn-salen modified metal-organic cages to achieve the structural regulation of cage compound,by using the differentiated host-guest electrostatic interactions of counter ions with metal-organic hosts.Compared to other anions,the presence of chloride ions caused the most significant fluorescence emission enhancement of Pd‑R(Zn),meanwhile,the UV-Vis absorption band attributed to the salen aromatic backbone showed an absorption decrease,and the metal-to-ligand induced peak displayed a blue shift effect.Circular dichro-ism and ^(1)H NMR spectra further demonstrate that the introduction of chloride anions is beneficial to keeping a more rigid scaffold.展开更多
Dimension-controllable supramolecular organic frameworks(SOFs)with aggregation-enhanced fluorescence are hierarchically fabricated through the host-guest interactions of cucurbit[8]uril(CB[8])and coumarin-modified tet...Dimension-controllable supramolecular organic frameworks(SOFs)with aggregation-enhanced fluorescence are hierarchically fabricated through the host-guest interactions of cucurbit[8]uril(CB[8])and coumarin-modified tetraphenylethylene derivatives(TPEC).The three-dimensional layered SOFs could be constructed from the further stacking of two-dimensional mono-layered structures via simply regulating the self-assembly conditions including the culturing time and concentration.Upon light irradiation under the wavelength of 365 nm,the photodimerization of coumarin moieties occurred,which resulted in the transformation of the resultant TPECn/CB[8]4n two-dimensional SOFs into robust covalently-connected 2D polymers with molecular thickness.Interestingly,the supramolecular system of TPEC/CB[8]exhibited intriguing multicolor fluorescence emission from yellow to blue in the time range of 0-24 h at 365 nm irradiation,possessing potential applicability for photochromic fluorescence ink.展开更多
文摘By virtue of a 3∶1 complementary coordination strategy,a chiral heteroleptic metal-organic cage that con-tains divergent functional units,Pd‑R(Zn),was precisely constructed via self-assembly of monodentate variational Zn-salen ligands RZn and NADH(reduced nicotinamide adenine dinucleotide)mimic modified tridentate ligands with square-planar Pd ions.UV-Vis and luminescence spectra experiments reveal that different anions could selec-tively interact with different sites of Zn-salen modified metal-organic cages to achieve the structural regulation of cage compound,by using the differentiated host-guest electrostatic interactions of counter ions with metal-organic hosts.Compared to other anions,the presence of chloride ions caused the most significant fluorescence emission enhancement of Pd‑R(Zn),meanwhile,the UV-Vis absorption band attributed to the salen aromatic backbone showed an absorption decrease,and the metal-to-ligand induced peak displayed a blue shift effect.Circular dichro-ism and ^(1)H NMR spectra further demonstrate that the introduction of chloride anions is beneficial to keeping a more rigid scaffold.
基金supported by Anhui Province Natural Science Funds(2008085QE209)K2020-03 from the State Key Laboratory of Molecular Engineering of Polymers(Fudan University)。
文摘Dimension-controllable supramolecular organic frameworks(SOFs)with aggregation-enhanced fluorescence are hierarchically fabricated through the host-guest interactions of cucurbit[8]uril(CB[8])and coumarin-modified tetraphenylethylene derivatives(TPEC).The three-dimensional layered SOFs could be constructed from the further stacking of two-dimensional mono-layered structures via simply regulating the self-assembly conditions including the culturing time and concentration.Upon light irradiation under the wavelength of 365 nm,the photodimerization of coumarin moieties occurred,which resulted in the transformation of the resultant TPECn/CB[8]4n two-dimensional SOFs into robust covalently-connected 2D polymers with molecular thickness.Interestingly,the supramolecular system of TPEC/CB[8]exhibited intriguing multicolor fluorescence emission from yellow to blue in the time range of 0-24 h at 365 nm irradiation,possessing potential applicability for photochromic fluorescence ink.