Herein,we prepared two novel pairs of enantiomeric gold cluster complexes,AU4PL4/Au4PD4 and(Au4L4)n/(Au4D4)n with atomic precision.In Au4PL4/Au4PD4,the discrete chiral Au4-based aggregation-induced emission(AIE)lumino...Herein,we prepared two novel pairs of enantiomeric gold cluster complexes,AU4PL4/Au4PD4 and(Au4L4)n/(Au4D4)n with atomic precision.In Au4PL4/Au4PD4,the discrete chiral Au4-based aggregation-induced emission(AIE)luminogens are separated by bulky substitutes.The corresponding aggregates are cyan-emitting with a photoluminescence quantum yield(PLQY)of 14.4%.Upon decreasing the size of the substituents,these chiral Au4 clusters are strung together by inter-cluster Au-Au interactions,which cause a low-energy green emission from the aggregated(Au4L4)n/(Au4D4)n with a much higher PLQY of 41.4%and more intense circularly polarised photoluminescence(CPL)with a dissymmetry factor|gPL|of 7.0×10^−3.Using(Au4L4)n/(Au4D4)n,circularly polarised organic light-emitting diodes(CP-OLEDs)were for the first time fabricated with|gEL|=|gPL|.These findings signify that inter-cluster metallophilic interactions are a new and important type of driving force for AIE and crystallization-induced emission(CIE),suggesting great potential of CPL-active metal clusters in CP-OLEDs.展开更多
Surface thiolates play important roles in evincing the structures and properties of thiolated metal nanoclusters—one type of recently emerging inorganic-organic hybrids,and thus the thiolate substitution,especially s...Surface thiolates play important roles in evincing the structures and properties of thiolated metal nanoclusters—one type of recently emerging inorganic-organic hybrids,and thus the thiolate substitution,especially single thiolate substitution,is highly desirable for subtly tailoring the structures and properties of metal nanoclusters.However,such a single-thiolate substituting is challenging,and its influence on the metal-metal and metal-sulfur bonds remains mysterious due to the absence of the singlethiolate-substituted structure.Here,we developed a combined method,concurrently synthesized the single-thiolate-substituted nanocluster and its parent nanocluster,and successfully resolved their structures by single crystal X-ray crystallography,which reveals that the single thiolate substitute has an obvious influence on the metal-metal and metal-sulfur bond lengths although it has no effect on the absorption profile.Interestingly,the metal-metal and metal-sulfur bonds show various thermal extensibility and even the negative thermal expansion phenomena of the Au–S bond were observed in the single-thiolate-substituted nanocluster.The bond length-related stability was also observed.Overall,this study highlights a novel synthesis method and offers novel structural insights and an in-depth structure-property correlation of thiolated metal nanoclusters.展开更多
The synthesis method and crystal structure of a novel Mo 3 cluster compound are reported. The results of structural analysis and the quantum calculation for the entire cluster molecule reveal that though two Mo 3 clus...The synthesis method and crystal structure of a novel Mo 3 cluster compound are reported. The results of structural analysis and the quantum calculation for the entire cluster molecule reveal that though two Mo 3 cluster units, which belong to two different kinds of structural type respectively, show an apparent ionic characteristic, the interaction between them via the bridging S atoms is still quite certain. The relationship between cluster electron counting and stability of the Mo 3 clusters are also primarily discussed.展开更多
基金This work was supported by the National Science Fund for Distinguished Young Scholars(No.21825106)the National Natural Science Foundation of China(No.21671175)+1 种基金the Program for Science&Technology Innovation Talents in Universities of Henan Province(No.164100510005)the Program for Innovative Research Team(in Science and Technology)in Universities of Henan Province(No.19IRTSTHN022)and Zhengzhou University.
文摘Herein,we prepared two novel pairs of enantiomeric gold cluster complexes,AU4PL4/Au4PD4 and(Au4L4)n/(Au4D4)n with atomic precision.In Au4PL4/Au4PD4,the discrete chiral Au4-based aggregation-induced emission(AIE)luminogens are separated by bulky substitutes.The corresponding aggregates are cyan-emitting with a photoluminescence quantum yield(PLQY)of 14.4%.Upon decreasing the size of the substituents,these chiral Au4 clusters are strung together by inter-cluster Au-Au interactions,which cause a low-energy green emission from the aggregated(Au4L4)n/(Au4D4)n with a much higher PLQY of 41.4%and more intense circularly polarised photoluminescence(CPL)with a dissymmetry factor|gPL|of 7.0×10^−3.Using(Au4L4)n/(Au4D4)n,circularly polarised organic light-emitting diodes(CP-OLEDs)were for the first time fabricated with|gEL|=|gPL|.These findings signify that inter-cluster metallophilic interactions are a new and important type of driving force for AIE and crystallization-induced emission(CIE),suggesting great potential of CPL-active metal clusters in CP-OLEDs.
基金supported by the National Natural Science Foundation of China (21925303,21829501,21771186,22171268,22171267,21971246)the Anhui Provincial Natural Science Foundation(2108085MB56)+1 种基金the HFIPS Director’s Fund (BJPY2019A02,YZJJ202102,YZJJ202306-TS)the Collaborative Innovation Program of Hefei Science Center,Chinese Academy of Sciences (2020HSC-CIP005,2022HSCCIP018)。
文摘Surface thiolates play important roles in evincing the structures and properties of thiolated metal nanoclusters—one type of recently emerging inorganic-organic hybrids,and thus the thiolate substitution,especially single thiolate substitution,is highly desirable for subtly tailoring the structures and properties of metal nanoclusters.However,such a single-thiolate substituting is challenging,and its influence on the metal-metal and metal-sulfur bonds remains mysterious due to the absence of the singlethiolate-substituted structure.Here,we developed a combined method,concurrently synthesized the single-thiolate-substituted nanocluster and its parent nanocluster,and successfully resolved their structures by single crystal X-ray crystallography,which reveals that the single thiolate substitute has an obvious influence on the metal-metal and metal-sulfur bond lengths although it has no effect on the absorption profile.Interestingly,the metal-metal and metal-sulfur bonds show various thermal extensibility and even the negative thermal expansion phenomena of the Au–S bond were observed in the single-thiolate-substituted nanocluster.The bond length-related stability was also observed.Overall,this study highlights a novel synthesis method and offers novel structural insights and an in-depth structure-property correlation of thiolated metal nanoclusters.
文摘The synthesis method and crystal structure of a novel Mo 3 cluster compound are reported. The results of structural analysis and the quantum calculation for the entire cluster molecule reveal that though two Mo 3 cluster units, which belong to two different kinds of structural type respectively, show an apparent ionic characteristic, the interaction between them via the bridging S atoms is still quite certain. The relationship between cluster electron counting and stability of the Mo 3 clusters are also primarily discussed.