A simple binary synthetic approach with variable[HCOOH]/[Th(IV)]ratios and the addition of water resulted in the self-assembly of six novel thorium formate complexes with well-controlled structures ranging from 0D clu...A simple binary synthetic approach with variable[HCOOH]/[Th(IV)]ratios and the addition of water resulted in the self-assembly of six novel thorium formate complexes with well-controlled structures ranging from 0D clusters and 2D layered networks to 3D frameworks.Specifically,small[HCOOH]/[Th(IV)]promoted the formation of the hexanuclear Th_(6)O_(4)(OH)_(4)(HCOO)_(12) core,a secondary building unit for the construction of 3D[Th_(6)Na(μ_(3)-O)_(4)(μ_(3)-OH)_(4)(HCOO)_(14)]·[NH_(2)(CH_(3))_(2)]·(DMF)_(3)(H_(2)O)_(5)(Th-SINAP-1),2D[Th_(6)(μ_(3)-O)_(4)(μ_(3)-OH)_(4)(HCOO)_(12)(DMF)_(2)]·(H_(2)O)_(10)(Th-SINAP-2),and 0D[Th_(6)(μ_(3)-O)_(4)(μ_(3)-OH)_(4)(HCOO)_(12)(H_(2)O)_(6)]·G(Th-SINAP-3).The large[HCOOH]/[Th(IV)]inhibited the olation/oxolation reaction,affording 3D frameworks of[Th_(2)(HCOO)_(9)]·[NH_(2)(CH_(3))_(2)]·(DMF)(H_(2)O)_(2)(Th-SINAP-4),[Th_(2)(HCOO)_(9)]·[NH_(2)(CH_(3))_(2)]·(DMF)(H_(2)O)_(4)(Th-SINAP-5),and[Th_(2)(HCOO)8(H_(2)O)(DMF)]·(H_(2)O)_(3)(Th-SINAP-6)with monomeric Th(IV)cations as the metal nodes.The addition of water not only affected the hydrolysis of Th(IV)to form nucleophilic hydroxo/oxo-aquo Th species,but also influenced the overall solid-state packing via the competition between H_(2)O,HCOO-,OH-/O_(2)-,and DMF for coordination with Th^(4+)cations.This unexpected structural complexity of thorium formates opens a new avenue for the targeted design and synthesis of atypical coordination polymers,e.g.open-framework materials of actinides,for applications in diverse fields such as radionuclide adsorption.展开更多
基金supported by grants from the National Natural Science Foundation of China(21876182,21701184,and 21906163).
文摘A simple binary synthetic approach with variable[HCOOH]/[Th(IV)]ratios and the addition of water resulted in the self-assembly of six novel thorium formate complexes with well-controlled structures ranging from 0D clusters and 2D layered networks to 3D frameworks.Specifically,small[HCOOH]/[Th(IV)]promoted the formation of the hexanuclear Th_(6)O_(4)(OH)_(4)(HCOO)_(12) core,a secondary building unit for the construction of 3D[Th_(6)Na(μ_(3)-O)_(4)(μ_(3)-OH)_(4)(HCOO)_(14)]·[NH_(2)(CH_(3))_(2)]·(DMF)_(3)(H_(2)O)_(5)(Th-SINAP-1),2D[Th_(6)(μ_(3)-O)_(4)(μ_(3)-OH)_(4)(HCOO)_(12)(DMF)_(2)]·(H_(2)O)_(10)(Th-SINAP-2),and 0D[Th_(6)(μ_(3)-O)_(4)(μ_(3)-OH)_(4)(HCOO)_(12)(H_(2)O)_(6)]·G(Th-SINAP-3).The large[HCOOH]/[Th(IV)]inhibited the olation/oxolation reaction,affording 3D frameworks of[Th_(2)(HCOO)_(9)]·[NH_(2)(CH_(3))_(2)]·(DMF)(H_(2)O)_(2)(Th-SINAP-4),[Th_(2)(HCOO)_(9)]·[NH_(2)(CH_(3))_(2)]·(DMF)(H_(2)O)_(4)(Th-SINAP-5),and[Th_(2)(HCOO)8(H_(2)O)(DMF)]·(H_(2)O)_(3)(Th-SINAP-6)with monomeric Th(IV)cations as the metal nodes.The addition of water not only affected the hydrolysis of Th(IV)to form nucleophilic hydroxo/oxo-aquo Th species,but also influenced the overall solid-state packing via the competition between H_(2)O,HCOO-,OH-/O_(2)-,and DMF for coordination with Th^(4+)cations.This unexpected structural complexity of thorium formates opens a new avenue for the targeted design and synthesis of atypical coordination polymers,e.g.open-framework materials of actinides,for applications in diverse fields such as radionuclide adsorption.
