Engineering ideal functional coordination polymers(CPs)via post-synthetic modification has emerged as a powerful synthetic strategy to achieve desirable functionalities and superior properties.In this work,we report a...Engineering ideal functional coordination polymers(CPs)via post-synthetic modification has emerged as a powerful synthetic strategy to achieve desirable functionalities and superior properties.In this work,we report a versatile ligand-strain modulation strategy that harnesses ligand strain to modify the skeleton conformation of CPs by metal node exchange.A one-dimensional(1D)crystalline CP,Ag(I)-L,featuring a curved ligand geometry,is prepared through a direct synthesis route.Exploiting polarization differences between different metal ions,we successfully regulate the ligand strain,enabling a metal node exchange process that yields another crystalline CP,Cu(I)-L,exhibiting a distinct linear parallel ligand orientation.Significantly,the complete exchange of AgNO_(3) to CuI is achieved via solid-liquid contact,while only partial exchange occurs under grinding.This ligand-strain engineering strategy will open new avenues in constructing functional systems and supramolecular materials through dynamic metal exchange and ligand-strain control.展开更多
Metal–metal(M–M)closed-shell interaction,also known as metallophilicity,is frequently observed in d^(10)and d^(8)metal complexes featuring a close M–M distance.It has shown a significant impact on diverse chemical ...Metal–metal(M–M)closed-shell interaction,also known as metallophilicity,is frequently observed in d^(10)and d^(8)metal complexes featuring a close M–M distance.It has shown a significant impact on diverse chemical systems,influencing structural,catalytic,and photophysical properties.The strength of both M–M interactions and the resulting M–M distances is highly dependent on various types of coordinating ligands.Recent studies have revealed that metallophilicity is repulsive in nature due to strong M–M Pauli repulsion(Q.Wan,J.Yang,W.-P.To and C.-M.Che,Strong metal–metal Pauli repulsion leads to repulsive metallophilicity in closed-shell d8 and d10 organometallic complexes,Proc.Natl.Acad.Sci.U.S.A.,2021,118,e2019265118).However,little is known about the role of ligands in M–M repulsions.Here,we elucidate how metal–ligand(M–L)coordination modulates M–M repulsion through two key mechanisms:π-backbonding andσ-donor interactions.By systematically evaluating ligands spanning a spectrum ofπ-accepting andσ-donating strengths,we uncover opposing ligand effects.Strongπ-backbonding weakens M–M Pauli repulsion,enabling shorter intermetallic distances,whereas theσ-donating interaction increases the repulsion,lengthening M–M contacts.These computational insights establish a ligand-design framework for tuning metallophilicity in closed-shell metal complexes and advance the fundamental understanding of M–M interactions from the perspective of M–L coordination.展开更多
基金the Natural Science Foundation of Jilin Province(No.20230101052JC)the National Natural Science Foundation of China(No.52173200)the Fundamental Research Funds for the Central Universities(No.2022-JCXK-13)for financial support.
文摘Engineering ideal functional coordination polymers(CPs)via post-synthetic modification has emerged as a powerful synthetic strategy to achieve desirable functionalities and superior properties.In this work,we report a versatile ligand-strain modulation strategy that harnesses ligand strain to modify the skeleton conformation of CPs by metal node exchange.A one-dimensional(1D)crystalline CP,Ag(I)-L,featuring a curved ligand geometry,is prepared through a direct synthesis route.Exploiting polarization differences between different metal ions,we successfully regulate the ligand strain,enabling a metal node exchange process that yields another crystalline CP,Cu(I)-L,exhibiting a distinct linear parallel ligand orientation.Significantly,the complete exchange of AgNO_(3) to CuI is achieved via solid-liquid contact,while only partial exchange occurs under grinding.This ligand-strain engineering strategy will open new avenues in constructing functional systems and supramolecular materials through dynamic metal exchange and ligand-strain control.
基金the startup fund(Project No.4933633 and 5501780)the Direct Grant supported by the Chinese University of Hong Kong,Hong Kong(Project No.4053703)+1 种基金the support from the Research Grants Council of Hong Kong under the Early Career Scheme(Project No.24305125)The authors thank the open fund(Project No.6907430)of the State Key Laboratory of Synthetic Chemistry.
文摘Metal–metal(M–M)closed-shell interaction,also known as metallophilicity,is frequently observed in d^(10)and d^(8)metal complexes featuring a close M–M distance.It has shown a significant impact on diverse chemical systems,influencing structural,catalytic,and photophysical properties.The strength of both M–M interactions and the resulting M–M distances is highly dependent on various types of coordinating ligands.Recent studies have revealed that metallophilicity is repulsive in nature due to strong M–M Pauli repulsion(Q.Wan,J.Yang,W.-P.To and C.-M.Che,Strong metal–metal Pauli repulsion leads to repulsive metallophilicity in closed-shell d8 and d10 organometallic complexes,Proc.Natl.Acad.Sci.U.S.A.,2021,118,e2019265118).However,little is known about the role of ligands in M–M repulsions.Here,we elucidate how metal–ligand(M–L)coordination modulates M–M repulsion through two key mechanisms:π-backbonding andσ-donor interactions.By systematically evaluating ligands spanning a spectrum ofπ-accepting andσ-donating strengths,we uncover opposing ligand effects.Strongπ-backbonding weakens M–M Pauli repulsion,enabling shorter intermetallic distances,whereas theσ-donating interaction increases the repulsion,lengthening M–M contacts.These computational insights establish a ligand-design framework for tuning metallophilicity in closed-shell metal complexes and advance the fundamental understanding of M–M interactions from the perspective of M–L coordination.
