The Synergistic Effect Of Metal Affinity And ?...? Action

Metallophilicity,that is,the interaction between metal and metal,refers to a non-covalent interaction due to the attraction between metal ions and metal ions in metal complexes containing IB area metals.The interaction narrows the distance between metals and metals.?…? interaction refers to a type of non-covalent interaction forces between conjugated aromatic rings and conjugated aromatic rings.From the previous work,there have been results showing that the face-to-face ?…? interaction between dimers and dimers repulse rather than support the interdimer metal-metal attractive interactions,although the conclusion is proved from the crystal configuration and theoretical calculations.However,with the continuous development of density functional methods,the calculation results of the predecessors have large errors and are full of contradictions,so the conclusion that the face-to-face ?…?interaction between dimers and dimers repulse rather than support the interdimer metal-metal attractive interactions also needs to be deliberated.Therefore,to further explore the synergistic effect of metallophilicity and ?…? interaction,and recommend a density functional method and basis set that are most suitable for the calculation of the interaction energy of such systems are the highlights of this paperIn this paper,11 different ligands of neutral metallophilic dimers of Cu,Ag,Au are selected.The overlapping and crossing structures form a small system,which are optimized at MP2/cc-pVTZ level to obtain their stable configurations.The calculation results of the interaction energy under CCSD(T)/CBS method are the standards.Many kins of usual density functional methods are used with the def2-QZVPP basis set.The BSSE and the deformation energy are ignored,and the intermolecular interaction energy of the system is calculated separately.Comparing the standards,there is found that for such systems,the recommended method for calculating the intermolecular interaction energy is coB97M-VThis paper selects the neutral,positive and negative Cu,Ag,Au metalophilic dimers with ?…? interaction,and draws the electrostatic potential diagram of the metalophilic monomer by calculating the electron density of the molecule,and analyzes the molecule electron density distribution from qualitative aspect.Secondly,the overlapping and crossing configurations of the positive and negative metalophilic dimers,the three structures of[C6F5MPy]2(Cu,Ag,Au)and[C6F5MTh]2(Cu,Ag,Au)in the neutral metalophilic dimers that are configuration A,stacking of positive potential pyridine or thiophene and negative potential pentafluorobenzene;configuration B,pyridine,thiophene and pentafluorobenzene staggered;configuration C,two of the same positive potential pyridine or thiophene stack,two pentafluorobenzene stacks with the same negative potential,are selected.They are optimized at the MP2/cc-pVDZ level to obtain a stable structure with the lowest total energy.And taking Cu,Ag,Au as the central atom of the neutral metalophilic dimer system as a representative,using SAPT2 with def2-TZVPP basis set to get the energy decomposition analysis of dimers,the study found that the dispersion-dominated ?…?interaction between the aromatic rings and the aromatic rings can not offset the increase in exchange rejection caused by the stacking of the same ligand ring,and thus cannot support the metallophilicity between Cu,Ag,and Au metals;and when the aromatic rings with different electrostatic properties are stacked,the synergy between the electrostatic effect and dispersion effect can make the ?…? interaction between the ligands and the ligands support this metallophilicity and make the systems more stable.