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Designable Al32‐Oxo Clusters with Hydrotalcite‐like Structures: Snapshots of Boundary Hydrolysis and Optical Limiting
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2020-11-30 , DOI: 10.1002/anie.202012919 Ya‐Jie Liu 1, 2 , Qiao‐Hong Li 1 , De‐Jing Li 1 , Xue‐Zhen Zhang 1 , Wei‐Hui Fang 1 , Jian Zhang 1
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2020-11-30 , DOI: 10.1002/anie.202012919 Ya‐Jie Liu 1, 2 , Qiao‐Hong Li 1 , De‐Jing Li 1 , Xue‐Zhen Zhang 1 , Wei‐Hui Fang 1 , Jian Zhang 1
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The hydrolysis of earth‐abundant AlIII has implications in mineral mimicry, geochemistry and environmental chemistry. Third‐order nonlinear optical (NLO) materials are important in modern chemistry due to their extensive optical applications. The assembly of AlIII ions with π‐conjugated carboxylate ligands is carried out and the hydrolysis and NLO properties of the resultant material are studied. A series of Al32‐oxo clusters with hydrotalcite‐like cores and π‐conjugated shells are isolated. X‐ray diffraction revealed boundary hydrolysis occurs at the equatorially unsaturated coordination sites of AlIII ions. Charge distribution analysis and DFT calculations support the proposed boundary substitution. The Al32‐oxo clusters possess a significant reverse saturable absorption (RSA) response with a minimal normalized transmittance up to 29 %, indicating they are suitable candidates for optical limiting (OL) materials. This work elucidates the hydrolysis of AlIII and provides insight into layered materials that also have strong boundary activity at the edges or corners.
中文翻译：
具有水滑石样结构的可设计Al32-Oxo团簇：边界水解和光学限制的快照
富含地球的Al III的水解作用对矿物模拟，地球化学和环境化学具有影响。由于其广泛的光学应用，三阶非线性光学（NLO）材料在现代化学中很重要。进行了具有π共轭羧酸酯配体的Al III离子的组装，并研究了所得材料的水解和NLO性质。分离出一系列具有水滑石样核和π共轭壳的Al 32-氧代簇。X射线衍射显示边界水解发生在Al III离子的赤道不饱和配位点。电荷分布分析和DFT计算支持拟议的边界替代。铝32-oxo团簇具有显着的反向饱和吸收（RSA）反应，最小归一化透射率高达29％，这表明它们是光学限制（OL）材料的合适候选者。这项工作阐明了Al III的水解作用，并提供了对在边缘或拐角处也具有强边界活性的层状材料的深入了解。
更新日期：2020-11-30
中文翻译：
具有水滑石样结构的可设计Al32-Oxo团簇：边界水解和光学限制的快照
富含地球的Al III的水解作用对矿物模拟，地球化学和环境化学具有影响。由于其广泛的光学应用，三阶非线性光学（NLO）材料在现代化学中很重要。进行了具有π共轭羧酸酯配体的Al III离子的组装，并研究了所得材料的水解和NLO性质。分离出一系列具有水滑石样核和π共轭壳的Al 32-氧代簇。X射线衍射显示边界水解发生在Al III离子的赤道不饱和配位点。电荷分布分析和DFT计算支持拟议的边界替代。铝32-oxo团簇具有显着的反向饱和吸收（RSA）反应，最小归一化透射率高达29％，这表明它们是光学限制（OL）材料的合适候选者。这项工作阐明了Al III的水解作用，并提供了对在边缘或拐角处也具有强边界活性的层状材料的深入了解。
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