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Updated: Sep 16, 2025
Author Spotlight: Accelerating Discovery in Microporous Material Chemistry
Published on: October 6, 2023
Molecular Engineering of Ionic Metal-Organic Frameworks via Ligand Conjugation Modulation for Tailored
Qi Wu1, Xinyu Gao1, Wenyan Zhang1
1Key Laboratory of Synthetic and Natural Functional Molecule of the Ministry of Education, College of Chemistry & Materials Science, Northwest University, Xi'an, 710127, P. R. China.
Abstract:
The rational design of metal-organic frameworks (MOFs) with tunable phosphorescence remains challenging due to limited understanding of ligand conjugation effects on excited-state dynamics. Herein, two isomorphic ionic MOFs (IMOF-DMF and IMOF-DEF) are constructed via in situ decarbonylation of DMF/DEF, leveraging guest-ion size to regulate ligand conjugation through modulation of pyridine ring dihedral angles. IMOF-DEF exhibits superior room-temperature phosphorescence (RTP) and temperature-dependent behavior. Mechanistic studies reveal that reduced conjugation enhances intersystem crossing (ISC) by strengthening spin-orbit coupling while minimizing the singlet-triplet energy gap (ΔEst). Furthermore, a dual-parameter anti-counterfeiting platform and flexible PVA hydrogel films enable advanced information encryption through temperature/time-resolved signals and triple-state lifetime encoding. This work establishes ligand conjugation engineering as a key strategy for tailoring MOF photophysics, linking molecular design to optoelectronic applications and security technologies.
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