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A dinuclear Cu(i)-mediated complex: Theoretical studies of the G2Cu24+ cluster ion
The Journal of Chemical Physics ( IF 4.4 ) Pub Date : 2018-10-09 , DOI: 10.1063/1.5038366
Guo-Jin Cao 1
Affiliation  

Recently, the T–Hg(ii)2–A base pair containing two equivalents of Hg(ii) has been prepared and characterized experimentally, which implies that there might exist considerable stable metal-mediated base pairs holding two neighbouring metal centers. Here we report a quantum chemical study on geometries, electronic structures, and bonding of various G2Cu24+ (G = guanine) isomers including one di-copper(i) unit. Different density functional methods [Becke 3-parameter-Lee-Yang-Parr, Perdew−Becke−Ernzerhof, Becke−Perdew, Density Functional Theory with Dispersion Corrections (DFT-D)] assign ambiguous relative energies to these isomers with the singlet and triplet states. High-level ab initio [domain-based local pair natural orbital (DLPNO) coupled-cluster with single and double excitations and DLPNO-coupled-cluster with single, double, and perturbative triple excitations] calculations confirm that the lowest-lying isomer of the G2Cu24+ ion has C2h symmetry with the singlet state and is comparable to the singly and doubly charged homologues (G2Cu2+ and G2Cu22+). The extended transition state (ETS)-natural orbitals for the chemical valence (ETS-NOCV) calculations point out that it has larger instantaneous interaction energy and bond dissociation energy than the corresponding singly and doubly charged complexes due to its relatively stronger attractive energies and weaker Pauli repulsion. The orbital interactions in the quadruply charged cluster chiefly come from Cu24+ ← G⋯G π donations. The results may help the understanding of the bonding properties of other potential metal-base pair complexes with the electron transfer.

中文翻译:

双核Cu(i)介导的络合物:G2Cu24 +团簇离子的理论研究

最近,已经制备并通过实验表征了包含两个当量Hg(ii)的T–Hg(ii2 –A碱基对,这暗示着可能存在大量稳定的金属介导的碱基对,它们持有两个相邻的金属中心。在这里,我们报告了有关一种包括一种双铜(i)的各种G 2 Cu 2 4+(G =鸟嘌呤)异构体的几何结构,电子结构和键合的量子化学研究。) 单元。不同的密度泛函方法[Becke 3-parameter-Lee-Yang-Parr,Perdew-Becke-Ernzerhof,Becke-Perdew,带色散校正的密度泛函理论(DFT-D)]为这些异构体的单重态和三重态分配了模糊的相对能状态。高级别的从头计算[具有单和双激发的基于域的局部对自然轨道(DLPNO)耦合簇和具有单,双和扰动三重激发的DLPNO耦合簇]计算证实了该原子中最低的异构体G 2 Cu 2 4+离子具有单峰态的C 2h对称性,可与单电荷和双电荷同系物(G 2 Cu 2 +和G 2 Cu 2 2+)。用于化学价(ETS-NOCV)计算的扩展跃迁状态(ETS)-自然轨道指出,由于其相对较强的吸引力和较小的能量,其瞬时相互作用能和键解离能比相应的单电荷和双电荷复合物大。保利推斥。四电荷簇中的轨道相互作用主要来自Cu 2 4+ ←G⋯Gπ捐赠。结果可能有助于理解其他潜在的金属-碱对配合物与电子转移的键合特性。
更新日期:2018-10-14
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