Exploring Charge Redistribution at the Cu/Co6Se8 Interface

被引：0

作者：

Krajewski, Sebastian M. ^{[1
]}

Love, Robert J. ^{[1
]}

Kephart, Jonathan A. ^{[1
]}

Boggiano, Andrew C. ^{[2
]}

La Pierre, Henry S. ^{[2
,3
,4
]}

Kaminsky, Werner ^{[1
]}

Velian, Alexandra ^{[1
]}

机构：

[1] Univ Washington, Dept Chem, Seattle, WA 98195 USA

[2] Georgia Inst Technol, Sch Chem & Biochem, Atlanta, GA 30332 USA

[3] Georgia Inst Technol, Sch Chem & Biochem, Atlanta, GA 30332 USA

[4] Georgia Inst Technol, Sch Mech Engn, Med Phys Program, Atlanta, GA 30332 USA

来源：

INORGANIC CHEMISTRY | 2024年 / 63卷 / 43期

基金：

美国国家卫生研究院; 美国国家科学基金会;

关键词：

VALENCE TAUTOMERISM; ELECTRONIC-STRUCTURE; CLUSTERS; DISPROPORTIONATION; COORDINATION; NANOCLUSTERS; REACTIVITY; SULFIDES; COMPLEX; BINDING;

D O I：

10.1021/acs.inorgchem.4c02639

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

This study investigates the electronic interactions and charge redistribution at the dopant-support interface using a Cu/Co6Se8 cluster construct. Specifically, the redox cluster series [Cu3Co6Se8L6](n) ([1-Cu-3](n); n = 0, -1, -2, -3; L = Ph(2)PNTol(-), Ph = phenyl, Tol = p-tolyl) spanning four distinct oxidation states is synthesized and characterized using a multitude of techniques, including multinuclear NMR, UV-vis, XANES, and X-ray crystallography. Structural investigations indicate that the clusters are isostructural and chiral, adopting a pseudo-D-3 symmetry. Paramagnetic P-31 NMR spectroscopy and solution-phase magnetic measurements together with DFT calculations are employed to interrogate the electronic structure and spin-state changes across the [1-Cu-3](3-) to 1-Cu-3 redox series, revealing that the copper edge sites retain a +1 oxidation state while the Co/Se core becomes increasingly oxidized, yielding a highly zwitterionic cluster.

引用

页码：20388 / 20397

页数：10