Protecting clusters from coalescing by ligands has been universally adopted in the chemical synthesis of atomically precise clusters.Apart from the stabilization role,the effect of ligands on the electronic properties...Protecting clusters from coalescing by ligands has been universally adopted in the chemical synthesis of atomically precise clusters.Apart from the stabilization role,the effect of ligands on the electronic properties of cluster cores in constructing superatoms,however,has not been well understood.In this letter,a comprehensive theoretical study about the effect of an organic ligand,methylated N-heterocyclic carbene(C_(5)N_(2)H_(8)),on the geometrical and electronic properties of the aluminum-based clusters XAl_(12)(X=Al,C and P)featuring different valence electron shells was conducted by utilizing the density functional theory(DFT)calculations.It was observed that the ligand can dramatically alter the electronic properties of these aluminum-based clusters while maintaining their structural stability.More intriguingly,different from classical superatom design strategies,the proposed ligation strategy was evidenced to possess the capability of remarkably reducing the ionization potentials(IP)of these clusters forming the ligated superalkalis,which is regardless of their shell occupancy.The charge transfer complex formed during the ligation process,which regulates the electronic spectrum through the electrostatic Coulomb potential,was suggested to be responsible for such an IP drop.The ligation strategy highlighted here may provide promising opportunities in realizing the superatom synthesis in the liquid phase.展开更多
Imidazole and benz-imidazole based different NHC ligands have been designed to synthesize a Cu(I)@NHC complex.Calculated vertical electron affinity suggests that all the ligands belong to a special type of molecule,su...Imidazole and benz-imidazole based different NHC ligands have been designed to synthesize a Cu(I)@NHC complex.Calculated vertical electron affinity suggests that all the ligands belong to a special type of molecule,superalkali,and shows a very good non linear optical activity.展开更多
基金supported by the Innovation Project of Jinan Science and Technology Bureau(No.2021GXRC032)the Taishan Scholars Project of Shandong Province(No.ts201712011)+4 种基金the National Natural Science Foundation of China(NSFC,Nos.92161101,21603119)the Natural Science Foundation of Shandong Province(No.ZR2020ZD35)the Shandong University Multidisciplinary Research and Innovation Team of Young Scholars(No.2020QNQT015)the Young Scholars Program of Shandong University(YSPSDU,No.2018WLJH48)the Fundamental Research Funds of Shandong University(No.2017TB003).
文摘Protecting clusters from coalescing by ligands has been universally adopted in the chemical synthesis of atomically precise clusters.Apart from the stabilization role,the effect of ligands on the electronic properties of cluster cores in constructing superatoms,however,has not been well understood.In this letter,a comprehensive theoretical study about the effect of an organic ligand,methylated N-heterocyclic carbene(C_(5)N_(2)H_(8)),on the geometrical and electronic properties of the aluminum-based clusters XAl_(12)(X=Al,C and P)featuring different valence electron shells was conducted by utilizing the density functional theory(DFT)calculations.It was observed that the ligand can dramatically alter the electronic properties of these aluminum-based clusters while maintaining their structural stability.More intriguingly,different from classical superatom design strategies,the proposed ligation strategy was evidenced to possess the capability of remarkably reducing the ionization potentials(IP)of these clusters forming the ligated superalkalis,which is regardless of their shell occupancy.The charge transfer complex formed during the ligation process,which regulates the electronic spectrum through the electrostatic Coulomb potential,was suggested to be responsible for such an IP drop.The ligation strategy highlighted here may provide promising opportunities in realizing the superatom synthesis in the liquid phase.
基金funded by the Department of Science and Technology(DST),Government of India,INSPIRE award no.IFA14-CH-151Recourses and computational facilities of National Institute of Technology Rourkela are also greatly acknowledged.L.J.K.and J.I.W.thank the National Science Foundation for grant support(CHE-1751370)as well as computational resources provided by the uHPC cluster,managed by the University of Houston and acquired through support from the NSF(MRI-1531814).
文摘Imidazole and benz-imidazole based different NHC ligands have been designed to synthesize a Cu(I)@NHC complex.Calculated vertical electron affinity suggests that all the ligands belong to a special type of molecule,superalkali,and shows a very good non linear optical activity.
