期刊
NEW JOURNAL OF CHEMISTRY
卷 35, 期 10, 页码 2245-2252出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c1nj20377k
关键词
-
资金
- French GENCI (Grand Equipement National de Calcul Intensif) centre [2010-86170]
The influences of an oxygen ligand on the structural, magnetic and electronic properties of octahedral niobium cluster-based oxides and oxychlorides are reported. The Nb-6 metal cluster is edge-bridged by twelve inner ligands and additionally bonded to six apical ligands to form (Nb6L12L6a)-L-i units (L = Cl, O) wherein oxygen and chlorine are perfectly ordered. Oxygen favours the interconnection of clusters via double Oi-a/Oa-i bridges in a similar way to the double Si-a/Sa-i bridges found in Chevrel phases based on face capped (Mo6L8L6a)-L-i units. Periodic density functional theory (DFT) calculations confirm that increasing the number of inner oxygen ligands at the expense of chlorine atoms favours the 14 metal-electron (ME) count per octahedral cluster unit. It is also shown that weak interactions occur between neighbouring clusters. Indeed, magnetic measurements performed on A(x)Nb(6)Cl(12)O(2) (A = Rb, x = 0.816(8); A = Cs, x = 1) series containing 15-ME species evidence antiferromagnetic interactions at low temperatures. Broken-symmetry DFT calculations of exchange parameters within spin dimer analysis confirm the experimental results.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据