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Halide Replacement with Complete Preservation of Crystal Lattice in Mixed‐Anion Lanthanide Oxyhalides
Author(s) -
Udayakantha Malsha,
Handy Joseph V.,
Davidson Rachel D.,
Kaur Jagjit,
Villalpando Graciela,
Zuin Lucia,
Chakraborty Sudip,
Banerjee Sarbajit
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202104231
Subject(s) - halide , chemistry , ion , crystal structure , tetragonal crystal system , single displacement reaction , metathesis , crystallography , lanthanide , excited state , lattice energy , inorganic chemistry , organic chemistry , atomic physics , polymerization , physics , polymer
Abstract A challenge in anion control in periodic solids is to preserve the crystal lattice while substituting for different anions of widely varying size and hardness. Post‐synthetic modification routes that place cations or anions in non‐equilibrium configurations are promising; however, such methods remain relatively unexplored for anion placement. Here, we report the synthesis of LaOI nanocrystals by a non‐hydrolytic sol‐gel condensation reaction and their transformation into LaOBr, LaOCl, and LaOF nanocrystals along hard–soft acid–base principles using post‐synthetic metathesis reactions with ammonium halides. Anion displacement proceeds along halide planes, preserving the tetragonal matlockite structure. Energy‐variant X‐ray excited optical luminesce signatures of alloyed Tb 3+ ‐ions is a sensitive quantum reporter of the preservation of the cation sublattice and hardening of the crystal structure upon anion replacement.