Four new coordination polymers,{[Cd(mbtx)(4OHphCOO)]NO_(3)}n(1),{[Zn(mbtx)(1,4-bdc)_(0.5)(H_(2)O)_(2)]·(1,4-bdc)_(0.5)·4H_(2)O}n(2),{[Cd2(mbtx)(5NO_(2)-bdc)_(2)(H_(2)O)_(3)]·4.5H_(2)O}n(3),and{[Zn(H_(2)...Four new coordination polymers,{[Cd(mbtx)(4OHphCOO)]NO_(3)}n(1),{[Zn(mbtx)(1,4-bdc)_(0.5)(H_(2)O)_(2)]·(1,4-bdc)_(0.5)·4H_(2)O}n(2),{[Cd2(mbtx)(5NO_(2)-bdc)_(2)(H_(2)O)_(3)]·4.5H_(2)O}n(3),and{[Zn(H_(2)O)6][Zn_(2)(mbtx)_(2)(btc)_(2)(H_(2)O)_(4)]·2H_(2)O}n(4)(mbtx=1,3-bis(4H-1,2,4-triazole)benzene,4OHphCOO-=p-hydroxybenzoate,1,4-bdc2-=1,4-benzenedicarboxylate,5NO_(2)-bdc2-=5-nitro-isophthalate,btc3-=1,3,5-benzenetricarboxylate),were synthesized under room temperature condition and characterized by single-crystal X-ray diffraction,elemental analyses,and powder X-ray diffraction.Single-crystal X-ray structural analysis shows that complexes 1 and 3 are 2D networks.In 1,the adjacent 2D networks are linked to a 3D network byπ-πstacking interaction.2 and 4 exhibit 1D chains,and the 1D chains are connected into a 3D network byπ-πstacking interaction and intermolecular hydrogen bond.Luminescence and thermogravimetric analysis of the four complexes were discussed.CCDC:2416406,1;2416407,2;2416408,3;2416409,4.展开更多
Passivating the surface defects of three-dimensional(3D)perovskite layers with two-dimensional(2D)perovskites is a critical strategy for achieving high efficiency and stability in perovskite solar cells.However,the dy...Passivating the surface defects of three-dimensional(3D)perovskite layers with two-dimensional(2D)perovskites is a critical strategy for achieving high efficiency and stability in perovskite solar cells.However,the dynamic evolution of 2D/3D interfaces under external stimuli such as thermal stress and long-term illumination significantly impacts device performance.In this study,we systematically investigate the role of intermolecular interactions in governing ion migration at 2D/3D interfaces by physically stacking three 2D perovskite,(BA)_(2)PbI_(4)(BA=butylammonium),(PEA)_(2)PbI_(4)(PEA=phenethylammonium),and(BDA)PbI_(4)(BDA=1,4-butane diammonium),with 3D perovskite-MAPbI_(3)(MA=methylammonium),followed by thermal annealing;and subsequent characterization was carried out using ultraviolet-visible(UV-Vis)absorption and femtosecond-transient absorption(fs-TA)spectra.Our findings reveal that small MA^(+)ions migrate from the 3D perovskite into the 2D perovskites,forming quasi-2D perovskites and introducing new decay pathways,while BA^(+)and PEA^(+)ions back-incorporate into the 3D lattice,causing a slight blue shift of 2-3 nm in exciton peaks.Notably,no significant ion migration is observed at the(BDA)PbI_(4)/MAPbI_(3)interface due to strong hydrogen bonds,demonstrating superior robustness against ion movement.Further analysis indicates that the stability of 2D/3D interface is governed by intermolecular interactions,following the order:hydrogen bonds>π-πstacking>van der Waals forces.These findings highlight the pivotal role of molecular interactions in modulating ion migration at 2D/3D interfaces and provide a clear design principle for constructing stable 2D/3D heterojunctions by selecting diammonium cations with robust hydrogen bonds,offering key insights for the rational design of stable perovskite interfaces.展开更多
Aggregation behavior of 5,10,15-tris(pentafluorophenyl)corrole (F15TPC), 5,10,15,20-tetra(pentafluoroph-enyl)porphyrin (F20TPP), and their copper complexes in DCM solution were investigated by using UV-Vis spectro-sco...Aggregation behavior of 5,10,15-tris(pentafluorophenyl)corrole (F15TPC), 5,10,15,20-tetra(pentafluoroph-enyl)porphyrin (F20TPP), and their copper complexes in DCM solution were investigated by using UV-Vis spectro-scopic method. F20TPP and F20TPPCu exhibited strong π-π stacking interactions in DCM, and the intermolecular dimerization constants turned out to be 1.82 × 103 and 17.2 × 103 L·mol-1 respectively. However, extinction coefficients of F15TPC and F15TPCCu at soret band remained unchanged with increasing in their concentrations from 1.0 to 40.0 μmol·L-1, indicating they remained monomeric in DCM solution. Based on DFT calculation and the π-π stacking geometries observed in crystal structures of metal octaethylcorrole complexes, destroy of π-π interactions in F15TPC and F15TPCCu may be understood by the electrostatic potential surfaces (EPS) features of the molecules and steric repulsions caused by the introducing of three phenyl at the meso- positions of corrole macrocycle.展开更多
文摘Four new coordination polymers,{[Cd(mbtx)(4OHphCOO)]NO_(3)}n(1),{[Zn(mbtx)(1,4-bdc)_(0.5)(H_(2)O)_(2)]·(1,4-bdc)_(0.5)·4H_(2)O}n(2),{[Cd2(mbtx)(5NO_(2)-bdc)_(2)(H_(2)O)_(3)]·4.5H_(2)O}n(3),and{[Zn(H_(2)O)6][Zn_(2)(mbtx)_(2)(btc)_(2)(H_(2)O)_(4)]·2H_(2)O}n(4)(mbtx=1,3-bis(4H-1,2,4-triazole)benzene,4OHphCOO-=p-hydroxybenzoate,1,4-bdc2-=1,4-benzenedicarboxylate,5NO_(2)-bdc2-=5-nitro-isophthalate,btc3-=1,3,5-benzenetricarboxylate),were synthesized under room temperature condition and characterized by single-crystal X-ray diffraction,elemental analyses,and powder X-ray diffraction.Single-crystal X-ray structural analysis shows that complexes 1 and 3 are 2D networks.In 1,the adjacent 2D networks are linked to a 3D network byπ-πstacking interaction.2 and 4 exhibit 1D chains,and the 1D chains are connected into a 3D network byπ-πstacking interaction and intermolecular hydrogen bond.Luminescence and thermogravimetric analysis of the four complexes were discussed.CCDC:2416406,1;2416407,2;2416408,3;2416409,4.
基金supported by the Beijing Natural Science Foundation(2252013)the National Natural Science Foundation of China(U2230203,12404491)+1 种基金the Beijing National Laboratory for Condensed Matter Physics(2024BNLCMPKF008)the Fundamental Research Funds for Central Universities.
文摘Passivating the surface defects of three-dimensional(3D)perovskite layers with two-dimensional(2D)perovskites is a critical strategy for achieving high efficiency and stability in perovskite solar cells.However,the dynamic evolution of 2D/3D interfaces under external stimuli such as thermal stress and long-term illumination significantly impacts device performance.In this study,we systematically investigate the role of intermolecular interactions in governing ion migration at 2D/3D interfaces by physically stacking three 2D perovskite,(BA)_(2)PbI_(4)(BA=butylammonium),(PEA)_(2)PbI_(4)(PEA=phenethylammonium),and(BDA)PbI_(4)(BDA=1,4-butane diammonium),with 3D perovskite-MAPbI_(3)(MA=methylammonium),followed by thermal annealing;and subsequent characterization was carried out using ultraviolet-visible(UV-Vis)absorption and femtosecond-transient absorption(fs-TA)spectra.Our findings reveal that small MA^(+)ions migrate from the 3D perovskite into the 2D perovskites,forming quasi-2D perovskites and introducing new decay pathways,while BA^(+)and PEA^(+)ions back-incorporate into the 3D lattice,causing a slight blue shift of 2-3 nm in exciton peaks.Notably,no significant ion migration is observed at the(BDA)PbI_(4)/MAPbI_(3)interface due to strong hydrogen bonds,demonstrating superior robustness against ion movement.Further analysis indicates that the stability of 2D/3D interface is governed by intermolecular interactions,following the order:hydrogen bonds>π-πstacking>van der Waals forces.These findings highlight the pivotal role of molecular interactions in modulating ion migration at 2D/3D interfaces and provide a clear design principle for constructing stable 2D/3D heterojunctions by selecting diammonium cations with robust hydrogen bonds,offering key insights for the rational design of stable perovskite interfaces.
文摘Aggregation behavior of 5,10,15-tris(pentafluorophenyl)corrole (F15TPC), 5,10,15,20-tetra(pentafluoroph-enyl)porphyrin (F20TPP), and their copper complexes in DCM solution were investigated by using UV-Vis spectro-scopic method. F20TPP and F20TPPCu exhibited strong π-π stacking interactions in DCM, and the intermolecular dimerization constants turned out to be 1.82 × 103 and 17.2 × 103 L·mol-1 respectively. However, extinction coefficients of F15TPC and F15TPCCu at soret band remained unchanged with increasing in their concentrations from 1.0 to 40.0 μmol·L-1, indicating they remained monomeric in DCM solution. Based on DFT calculation and the π-π stacking geometries observed in crystal structures of metal octaethylcorrole complexes, destroy of π-π interactions in F15TPC and F15TPCCu may be understood by the electrostatic potential surfaces (EPS) features of the molecules and steric repulsions caused by the introducing of three phenyl at the meso- positions of corrole macrocycle.
