Local Coordination Disorder and Defect Formation in Cadmium Zeolitic Imidazolate Framework Glasses.
- 1Sao Carlos Institute of Physics, University of Sao Paulo, IFSC - USP, 13566-590Sao Carlos, SP, Brazil.
- 2Eduard-Zintl-Institute of Inorganic and Physical Chemistry, Technical University of Darmstadt, Peter-Grünberg-Straße 8, DarmstadtD-64287, Germany.
- 3Department of Chemistry, Physical Chemistry, University Paderborn, Warburger Straße 100, PaderbornD-33098, Germany.
Abstract
Cadmium-based zeolitic imidazolate glasses provide an attractive model system for investigating local coordination changes during vitrification. Here, we examine the structure of Cd(Im)2-x(bIm)x (Im = imidazolate, bIm = benzimidazolate) in its as-synthesized and glassy states using solid-state NMR spectroscopy, differential scanning calorimetry, electron paramagnetic resonance, and complementary techniques. Increasing bIm content reduces crystallinity and suppresses recrystallization, promoting glass formation. While 13C and 1H NMR spectra indicate largely preserved linker environments, broadening of 15N and 113Cd resonances reveals increased local disorder. 113Cd{1H} REDOR measurements show that the average 113Cd-1H dipolar interaction is largely preserved upon vitrification. Thus, the predominant local Cd coordination environment is retained, although minor coordination defects cannot be excluded. EPR reveals thermally induced paramagnetic centers, whose microscopic origin remains unassigned and may include coordination-related defects and thermal decomposition. Variable-temperature 1H NMR further reveals dynamic changes across the glass-transition region. Overall, ligand chemistry influences melting, recrystallization, and glass formation in hybrid coordination networks. Vitrification combines the preservation of the predominant local Cd environment with an increase in local geometric disorder and the formation of thermally induced paramagnetic centers.
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BibTeX
@article{filho2026local,
title = {{Local Coordination Disorder and Defect Formation in Cadmium Zeolitic Imidazolate Framework Glasses.}},
author = {Renato Pereira Murback Filho and Bruno Trebbi and Ricardo José da Silva Afonso and Camila Mizuki Ito Nishida and Jonas Lins and Gerd Buntkowsky and Torsten Gutmann and Eduardo Ribeiro deAzevedo and Marcos de Oliveira Junior},
journal = {Inorganic chemistry},
year = {2026},
month = oct,
doi = {10.1021/acs.inorgchem.6c03271},
url = {https://europepmc.org/article/MED/42916330},
note = {CC BY},
}
RIS
TY - JOUR
TI - Local Coordination Disorder and Defect Formation in Cadmium Zeolitic Imidazolate Framework Glasses.
AU - Renato Pereira Murback Filho
AU - Bruno Trebbi
AU - Ricardo José da Silva Afonso
AU - Camila Mizuki Ito Nishida
AU - Jonas Lins
AU - Gerd Buntkowsky
AU - Torsten Gutmann
AU - Eduardo Ribeiro deAzevedo
AU - Marcos de Oliveira Junior
PY - 2026
DA - 2026/10/01
JO - Inorganic chemistry
DO - 10.1021/acs.inorgchem.6c03271
UR - https://europepmc.org/article/MED/42916330
AB - Cadmium-based zeolitic imidazolate glasses provide an attractive model system for investigating local coordination changes during vitrification. Here, we examine the structure of Cd(Im)2-x(bIm)x (Im = imidazolate, bIm = benzimidazolate) in its as-synthesized and glassy states using solid-state NMR spectroscopy, differential scanning calorimetry, electron paramagnetic resonance, and complementary techniques. Increasing bIm content reduces crystallinity and suppresses recrystallization, promoting glass formation. While 13C and 1H NMR spectra indicate largely preserved linker environments, broadening of 15N and 113Cd resonances reveals increased local disorder. 113Cd{1H} REDOR measurements show that the average 113Cd-1H dipolar interaction is largely preserved upon vitrification. Thus, the predominant local Cd coordination environment is retained, although minor coordination defects cannot be excluded. EPR reveals thermally induced paramagnetic centers, whose microscopic origin remains unassigned and may include coordination-related defects and thermal decomposition. Variable-temperature 1H NMR further reveals dynamic changes across the glass-transition region. Overall, ligand chemistry influences melting, recrystallization, and glass formation in hybrid coordination networks. Vitrification combines the preservation of the predominant local Cd environment with an increase in local geometric disorder and the formation of thermally induced paramagnetic centers.
SN - 0020-1669
SN - 1520-510X
ER -