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Low-dimensional quantum spin systems with the Cu2+ central ion are still in the focus of experimental and theoretical research. Here is reported on growth of mm-sized single-crystals of the low-dimensional S = 1/2 spin compound Cu6(Ge,Si)6O18·6H2O by a diffusion technique in aqueous solution. A route to form Si-rich crystals down to possible dioptase, the pure silicate, is discussed. Motivated by previously reported incorrect assignments of UV-VIS spectra, the assignment of dd excitations from such spectra of the hexahydrate and the fully dehydrated compound is proposed in comparison to dioptase and selected Cu(II) oxo-compounds using bond strength considerations. Non-doped cuprates as layer compounds show higher excitation energies than the title compound. However, when the antiferromagnetic interaction energy as Jz·ln(2) is taken into account for cuprates, a single linear relationship between the Dqe excitation energy and equatorial Cu(II)-O bond strength is confirmed for all compounds. A linear representation is also confirmed between 2A1g energies and a function of axial and equatorial Cu-O bond distances if auxiliary axial bonds are used for four-coordinated compounds. The quotient Dt/Ds of experimental orbital energies deviating from the general trend to smaller values indicates the existence of H2O respectively Cl−axial ligands in comparison to oxo-ligands, whereas larger Dt/Dqe values indicate missing axial bonds. The quotient of the excitation energy 2A1g by 2·2Eg-2B2g allows checking for correctness of the assignment and to distinguish between axial oxo-ligands and others like H2O or Cl−.
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篇名 Crystal Growth of Cu6(Ge,Si)6O18·6H2O and Assignment of UV-VIS Spectra in Comparison to Dehydrated Dioptase and Selected Cu(II) Oxo-Compounds Including Cuprates
来源期刊 凝固态物理国际期刊(英文) 学科 化学
关键词 Dioptase Ge-Dioptase Copper(II) COMPOUNDS CUPRATES Crystal Growth UV-VIS Spectroscopy EPR Color d-d EXCITATIONS Bond Strength Super-Exchange Interaction
年,卷(期) 2017,(3) 所属期刊栏目
研究方向 页码范围 57-79
页数 23页 分类号 O6
字数 语种
DOI
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Dioptase
Ge-Dioptase
Copper(II)
COMPOUNDS
CUPRATES
Crystal
Growth
UV-VIS
Spectroscopy
EPR
Color
d-d
EXCITATIONS
Bond
Strength
Super-Exchange
Interaction
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研究去脉
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期刊影响力
凝固态物理国际期刊(英文)
季刊
2160-6919
武汉市江夏区汤逊湖北路38号光谷总部空间
出版文献量(篇)
215
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0
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