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Designable Al 32 ‐Oxo Clusters with Hydrotalcite‐like Structures: Snapshots of Boundary Hydrolysis and Optical Limiting
Author(s) -
Liu YaJie,
Li QiaoHong,
Li DeJing,
Zhang XueZhen,
Fang WeiHui,
Zhang Jian
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202012919
Subject(s) - hydrolysis , hydrotalcite , conjugated system , ion , absorption (acoustics) , carboxylate , deprotonation , chemistry , materials science , computational chemistry , inorganic chemistry , chemical physics , organic chemistry , polymer , catalysis , composite material
The hydrolysis of earth‐abundant Al III 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 Al III ions with π‐conjugated carboxylate ligands is carried out and the hydrolysis and NLO properties of the resultant material are studied. A series of Al 32 ‐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 Al III ions. Charge distribution analysis and DFT calculations support the proposed boundary substitution. The Al 32 ‐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 Al III and provides insight into layered materials that also have strong boundary activity at the edges or corners.