Metallophilic interaction is a unique type of weak intermolecular interaction,where the electronic configuration of two metal atoms is closed shell.Despite its significance in multidisciplinary fields,the nature of me...Metallophilic interaction is a unique type of weak intermolecular interaction,where the electronic configuration of two metal atoms is closed shell.Despite its significance in multidisciplinary fields,the nature of metallophilic interaction is still not well understood.In this work,we investigated the electronic structures and bonding characteristic of bimetallic Au2@Cu6 nanocluster through density functional theory method,which was reported in experiments recently[Angew.Chem.Int.Ed.55,3611(2016)].In general thinking,interaction between two moieties of(CuSH)6 ring and(Au2PH3)2 in the Au2@Cu6 nanocluster can be viewed as a d^10-σ closed-shell interaction.However,chemical bonding analysis shows that there is a ten center-two electron(10c-2e)multicenter bonding between two moieties.Further comparative studies on other bimetallic nanocluster M2@Cu6(M=Ag,Cu,Zn,Cd,Hg)also revealed that multicenter bonding is the origin of electronic stability of the complexes besides the d10-σclosed-shell interaction.This will provide valuable insights into the understanding of closed-shell interactions.展开更多
Laser ablated boron atoms have been reacted with hydrogen sulfide and the reaction products condensed with argon at 4 K, which gave BS2, BS2-, HSBS, and HBS molecules. Reagent isotopic substitution （H2S, H234S, D2S, ...Laser ablated boron atoms have been reacted with hydrogen sulfide and the reaction products condensed with argon at 4 K, which gave BS2, BS2-, HSBS, and HBS molecules. Reagent isotopic substitution （H2S, H234S, D2S, 10 B, 11B） and variation of boron and hydrogen sulfide concentrations have been used to identify the major products. Both BS2-- and BS2 were identified as linear molecules with no significant difference in the structure parameters, but the B-S anti-symmetric stretching vibration of BS2 is significantly lower than that of BS2-, which is ascribed to pseudo Jahn-Teller effect. Theoretical calculation was employed to have an insight into the interaction nature of the bonds in the corresponding products.展开更多
基金supported by the National Natural Science Foundation of China(No.21873001 and No.21873002)the Foundation of Distinguished Young Scientists of Anhui Province。
文摘Metallophilic interaction is a unique type of weak intermolecular interaction,where the electronic configuration of two metal atoms is closed shell.Despite its significance in multidisciplinary fields,the nature of metallophilic interaction is still not well understood.In this work,we investigated the electronic structures and bonding characteristic of bimetallic Au2@Cu6 nanocluster through density functional theory method,which was reported in experiments recently[Angew.Chem.Int.Ed.55,3611(2016)].In general thinking,interaction between two moieties of(CuSH)6 ring and(Au2PH3)2 in the Au2@Cu6 nanocluster can be viewed as a d^10-σ closed-shell interaction.However,chemical bonding analysis shows that there is a ten center-two electron(10c-2e)multicenter bonding between two moieties.Further comparative studies on other bimetallic nanocluster M2@Cu6(M=Ag,Cu,Zn,Cd,Hg)also revealed that multicenter bonding is the origin of electronic stability of the complexes besides the d10-σclosed-shell interaction.This will provide valuable insights into the understanding of closed-shell interactions.
文摘Laser ablated boron atoms have been reacted with hydrogen sulfide and the reaction products condensed with argon at 4 K, which gave BS2, BS2-, HSBS, and HBS molecules. Reagent isotopic substitution （H2S, H234S, D2S, 10 B, 11B） and variation of boron and hydrogen sulfide concentrations have been used to identify the major products. Both BS2-- and BS2 were identified as linear molecules with no significant difference in the structure parameters, but the B-S anti-symmetric stretching vibration of BS2 is significantly lower than that of BS2-, which is ascribed to pseudo Jahn-Teller effect. Theoretical calculation was employed to have an insight into the interaction nature of the bonds in the corresponding products.
