TY - JOUR

T1 - Modulating Room-Temperature Phosphorescence by Coordination Interactions and Structural Rigidity in Dual-Ligand MOFs

AU - Yu, Xiaolin

AU - Zhou, Zixuan

AU - Pavlov, Dmitry I.

AU - Bereznikov, Nikita V.

AU - Pavlova, Vladislava V.

AU - Dudko, Evgeny R.

AU - Ryadun, Alexey A.

AU - Benassi, Enrico

AU - Milichko, Valentin A.

AU - Tao, Shengyang

AU - Potapov, Andrei S.

AU - Fedin, Vladimir P.

N1 - This work was supported by the Fundamental Research Funds for the Central Universities under Grant No. DUT25RC(3)042. E.B. acknowledges the support received by the Ministry of Science and Higher Education of the Russian Federation (project No. FSER-2024-0003) and ITMO Fellowship Program for infrastructural support. NIIC analytical facilities used in this work operate with support from the Ministry of Science and Higher Education of the Russian Federation (project No. FWUZ-2025-0001).

PY - 2026/7/27

Y1 - 2026/7/27

N2 - The development of room-temperature phosphorescent (RTP) functional materials based on metal–organic frameworks (MOFs) is of great significance for fundamental photophysical studies as well as applications in information encryption and anticounterfeiting. However, the regulatory mechanisms of coordination interactions and structural rigidity on the RTP behavior in MOFs remain poorly understood. In this study, a dual-ligand cooperative design strategy (M + LC + LX) was implemented, in which the direct coordination of the carboxylate ligand to the metal center and the rigidity of the framework were systematically modulated. Four novel Cd-MOFs were successfully constructed, achieving precise control over the RTP performance. SCXRD analysis combined with DFT calculations revealed that the direct coordination of LC is essential for RTP activation, whereas the framework dimensionality and the suppression of terminal vibrational relaxation imparted by the auxiliary ligand predominantly govern the extension of triplet-state lifetimes up to 153 ms. In addition, by exploiting the distinct afterglow differences and time-dependent color evolution, a time-resolved information encryption and anticounterfeiting strategy was devised, greatly enhancing information security. This study for the first time elucidates the synergistic mechanism of coordination interactions and structural rigidity on RTP behavior in MOFs and provides insights for the rational design of high-performance RTP functional materials.

AB - The development of room-temperature phosphorescent (RTP) functional materials based on metal–organic frameworks (MOFs) is of great significance for fundamental photophysical studies as well as applications in information encryption and anticounterfeiting. However, the regulatory mechanisms of coordination interactions and structural rigidity on the RTP behavior in MOFs remain poorly understood. In this study, a dual-ligand cooperative design strategy (M + LC + LX) was implemented, in which the direct coordination of the carboxylate ligand to the metal center and the rigidity of the framework were systematically modulated. Four novel Cd-MOFs were successfully constructed, achieving precise control over the RTP performance. SCXRD analysis combined with DFT calculations revealed that the direct coordination of LC is essential for RTP activation, whereas the framework dimensionality and the suppression of terminal vibrational relaxation imparted by the auxiliary ligand predominantly govern the extension of triplet-state lifetimes up to 153 ms. In addition, by exploiting the distinct afterglow differences and time-dependent color evolution, a time-resolved information encryption and anticounterfeiting strategy was devised, greatly enhancing information security. This study for the first time elucidates the synergistic mechanism of coordination interactions and structural rigidity on RTP behavior in MOFs and provides insights for the rational design of high-performance RTP functional materials.

UR - https://www.scopus.com/pages/publications/105045825092

UR - https://www.mendeley.com/catalogue/8d84bde7-030b-3215-aae6-bf64eb5b79b7/

U2 - 10.1021/acs.inorgchem.5c06044

DO - 10.1021/acs.inorgchem.5c06044

M3 - Article

C2 - 41700125

VL - 65

SP - 16652

EP - 16662

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 29

ER -