A series of 1D coordination polymers(CPs),[MnX_(2)(L)]_(n)(X=Cl,Br,I),made of MnX_(2)units bridged by 1,7-[Ph_(2)P(O)]_(2)-meta-carborane ligands(L)through the O-Mn-O linkages,have been designed.At ambient temperature...A series of 1D coordination polymers(CPs),[MnX_(2)(L)]_(n)(X=Cl,Br,I),made of MnX_(2)units bridged by 1,7-[Ph_(2)P(O)]_(2)-meta-carborane ligands(L)through the O-Mn-O linkages,have been designed.At ambient temperature,these CPs manifest green phosphorescence with quantum yields of up to 60%,which is the highest value for Mn(II)CPs.CP[MnI_(2)(L)]_(n)and its structurally different solvate[MnI_(2)(L)·CH_(2)Cl_(2)]_(n)also exhibit bright triboluminescence.Thermochromic luminescence of the designed CPs appears as reversible shifting of their emission color,when the temperature varies from 350 to 77 K and back.Moreover,[MnI_(2)(L)·CH_(2)Cl_(2)]_(n)reversibly changes its emission properties during desolvation-solvation processes thus featuring solvatochromic luminescence.According to photophysical and EPR data,the observed phosphorescence originates from the ligand-sensitized^(4)T_(1)→^(6)A_(1)transition in Mn^(2+)ions.Enhanced robustness of the title CPs is demonstrated by retaining their emission properties after prolonged heating at 210°C.展开更多
In the quest for organic–inorganic metal halides(OIMHs)that harmoniously combine large second harmonic generation(SHG)efficiency with broad bandgaps,our study introduces a series of noncentrosymmetric and polar piper...In the quest for organic–inorganic metal halides(OIMHs)that harmoniously combine large second harmonic generation(SHG)efficiency with broad bandgaps,our study introduces a series of noncentrosymmetric and polar piperazine zinc halides,(C_(4)H_(11)N_(2))ZnX_(3)(X=Cl,Br,I).The distinct influence of halide anion size on the configuration of ZnNX_(3)tetrahedra is uncovered,revealing a design principle for enhancing SHG activity and manipulating bandgap characteristics.Specifically,(C_(4)H_(11)N_(2))ZnCl_(3)is the first example of deep-ultraviolet(deep-UV)nonlinear optical(NLO)OIMHs,with UV transparency lower than 190 nm and moderate SHG effect,0.8 times KH_(2)PO_(4)(KDP).Meanwhile,compared with(C_(4)H_(11)N_(2))ZnI_(3)(2.1 times KDP,4.52 eV),(C_(4)H_(11)N_(2))ZnBr_(3)boasts a widened bandgap of 5.53 eV while maintaining a striking SHG response(2.5 times KDP),representing a pinnacle in the SHG-bandgap balance among OIMHs with Eg exceeding 5.0 eV.Computational analyses underscore the critical roles of halide orbitals and ZnNX_(3)distortions in dictating SHG efficiency,with increasing halide polarizability correlating with heightened SHG contributions.This study paves the way for a novel approach to designing short-UV NLO crystals based on OIMHs.展开更多
基金Russian Foundation for Basic Research(Project No.18-03-00300)。
文摘A series of 1D coordination polymers(CPs),[MnX_(2)(L)]_(n)(X=Cl,Br,I),made of MnX_(2)units bridged by 1,7-[Ph_(2)P(O)]_(2)-meta-carborane ligands(L)through the O-Mn-O linkages,have been designed.At ambient temperature,these CPs manifest green phosphorescence with quantum yields of up to 60%,which is the highest value for Mn(II)CPs.CP[MnI_(2)(L)]_(n)and its structurally different solvate[MnI_(2)(L)·CH_(2)Cl_(2)]_(n)also exhibit bright triboluminescence.Thermochromic luminescence of the designed CPs appears as reversible shifting of their emission color,when the temperature varies from 350 to 77 K and back.Moreover,[MnI_(2)(L)·CH_(2)Cl_(2)]_(n)reversibly changes its emission properties during desolvation-solvation processes thus featuring solvatochromic luminescence.According to photophysical and EPR data,the observed phosphorescence originates from the ligand-sensitized^(4)T_(1)→^(6)A_(1)transition in Mn^(2+)ions.Enhanced robustness of the title CPs is demonstrated by retaining their emission properties after prolonged heating at 210°C.
基金supported by the National Natural Science Foundation of China(No.22205037 and 22373014)Natural Science Foundation of Fujian Province(2023J01498).
文摘In the quest for organic–inorganic metal halides(OIMHs)that harmoniously combine large second harmonic generation(SHG)efficiency with broad bandgaps,our study introduces a series of noncentrosymmetric and polar piperazine zinc halides,(C_(4)H_(11)N_(2))ZnX_(3)(X=Cl,Br,I).The distinct influence of halide anion size on the configuration of ZnNX_(3)tetrahedra is uncovered,revealing a design principle for enhancing SHG activity and manipulating bandgap characteristics.Specifically,(C_(4)H_(11)N_(2))ZnCl_(3)is the first example of deep-ultraviolet(deep-UV)nonlinear optical(NLO)OIMHs,with UV transparency lower than 190 nm and moderate SHG effect,0.8 times KH_(2)PO_(4)(KDP).Meanwhile,compared with(C_(4)H_(11)N_(2))ZnI_(3)(2.1 times KDP,4.52 eV),(C_(4)H_(11)N_(2))ZnBr_(3)boasts a widened bandgap of 5.53 eV while maintaining a striking SHG response(2.5 times KDP),representing a pinnacle in the SHG-bandgap balance among OIMHs with Eg exceeding 5.0 eV.Computational analyses underscore the critical roles of halide orbitals and ZnNX_(3)distortions in dictating SHG efficiency,with increasing halide polarizability correlating with heightened SHG contributions.This study paves the way for a novel approach to designing short-UV NLO crystals based on OIMHs.
