Four novel uranyl coordination polymers,UO_(2)(bcH_(2)ba)(bcNOba)_(0.5)(1),UO_(2)(bcNOba)(H_(2)O)(2),UO_(2)(bcNOba)(phen)(3)and UO_(2)(bcH_(2)ba)_(2)[phen](4)(H_(2)bcHba=4,4'-(azanediylbis(methylene))dibenzoic aci...Four novel uranyl coordination polymers,UO_(2)(bcH_(2)ba)(bcNOba)_(0.5)(1),UO_(2)(bcNOba)(H_(2)O)(2),UO_(2)(bcNOba)(phen)(3)and UO_(2)(bcH_(2)ba)_(2)[phen](4)(H_(2)bcHba=4,4'-(azanediylbis(methylene))dibenzoic acid;phen=1,10-phenanthroline),were successfully synthesized through hydrothermal reactions.Interestingly,in situ nitrosylation of the secondary amine group was observed in the presence of nitric acid.This reactivity could serve as a platform for the synthesis of different novel uranyl coordination polymers.This work presents three possible pathways that could exist in the in situ reaction system.In compound 4,only the ligand that did not undergo in situ reaction(bcH_(2)ba^(-))was involved in the compound construction,in which the adjacent uranyl ions are bridged by two bcH_(2)ba^(-)ligands,and can be extended into a two-strand 1D chain structure.In compounds 2 and 3,only the ligand that underwent in situ reaction(bcNOba^(2-))participated in the compound build-up and the two compounds both featured 1D chain structures.Interestingly,ligands with and without in situ reaction both participated in the construction of compound 1 which possessed one uranyl ion,one bcH_(2)ba^(-)ligand and half a bcNOba^(2-)ligand,and could be further extended to a 3D porous helical framework.The 3D structure of compound 1 was defined by intertwining and interpenetrating six equivalent 3D porous helical frameworks.Structural analysis of these uranyl compounds revealed that the introduction of a nitroso group exerted significant influences on the conformations of ligands,skeletons and 3D structures.Furthermore,theoretical calculations using relativistic density functional theory were also performed to explore the electronic structure and bonding nature of these uranyl compounds.展开更多
基金Science Challenge Project(TZ2016004)National Natural Science Foundation of China(No.21701178,21671191,11875058)。
文摘Four novel uranyl coordination polymers,UO_(2)(bcH_(2)ba)(bcNOba)_(0.5)(1),UO_(2)(bcNOba)(H_(2)O)(2),UO_(2)(bcNOba)(phen)(3)and UO_(2)(bcH_(2)ba)_(2)[phen](4)(H_(2)bcHba=4,4'-(azanediylbis(methylene))dibenzoic acid;phen=1,10-phenanthroline),were successfully synthesized through hydrothermal reactions.Interestingly,in situ nitrosylation of the secondary amine group was observed in the presence of nitric acid.This reactivity could serve as a platform for the synthesis of different novel uranyl coordination polymers.This work presents three possible pathways that could exist in the in situ reaction system.In compound 4,only the ligand that did not undergo in situ reaction(bcH_(2)ba^(-))was involved in the compound construction,in which the adjacent uranyl ions are bridged by two bcH_(2)ba^(-)ligands,and can be extended into a two-strand 1D chain structure.In compounds 2 and 3,only the ligand that underwent in situ reaction(bcNOba^(2-))participated in the compound build-up and the two compounds both featured 1D chain structures.Interestingly,ligands with and without in situ reaction both participated in the construction of compound 1 which possessed one uranyl ion,one bcH_(2)ba^(-)ligand and half a bcNOba^(2-)ligand,and could be further extended to a 3D porous helical framework.The 3D structure of compound 1 was defined by intertwining and interpenetrating six equivalent 3D porous helical frameworks.Structural analysis of these uranyl compounds revealed that the introduction of a nitroso group exerted significant influences on the conformations of ligands,skeletons and 3D structures.Furthermore,theoretical calculations using relativistic density functional theory were also performed to explore the electronic structure and bonding nature of these uranyl compounds.
