TY - JOUR
T1 - Directional Exciton Migration in Benzoimidazole-Based Metal–Organic Frameworks
AU - Gutierrez Arzaluz, Luis
AU - Jia, Jiangtao
AU - Gu, Chun
AU - Czaban-Jozwiak, Justyna
AU - Yin, Jun
AU - Shekhah, Osama
AU - Bakr, Osman
AU - Eddaoudi, Mohamed
AU - Mohammed, Omar F.
N1 - KAUST Repository Item: Exported on 2021-05-27
Acknowledged KAUST grant number(s): CARF-FCC/1/1972-63-01
Acknowledgements: The authors thank King Abdullah University of Science and Technology (KAUST) and the CARF-FCC/1/1972-63-01 project for financial support and the Supercomputing Laboratory at KAUST for computational and storage resources.
PY - 2021/5/19
Y1 - 2021/5/19
N2 - Highly luminescent metal-organic frameworks (MOFs) have recently received great attention due to their potential applications as sensors and light-emitting devices. In these MOFs, the highly ordered fluorescent organic linkers positioning prevents excited-state self-quenching and rotational motion, enhancing their light-harvesting properties. Here, the exciton migration between the organic linkers with the same chemical structure but different protonation degrees in Zr-based MOFs was explored and deciphered using ultrafast laser spectroscopy and density functional theory calculations. First, we clearly demonstrate how hydrogen-bonding interactions between free linkers and solvents affect the twisting changes, internal conversion processes, and luminescent behavior of a benzoimidazole-based linker. Second, we provide clear evidence of an ultrafast energy transfer between well-aligned adjacent linkers with different protonation states inside the MOF. These findings provide a new fundamental photophysical insight into the exciton migration dynamics between linkers with different protonation states coexisting at different locations in MOFs and serve as a benchmark for improving light-harvesting MOF architectures.
AB - Highly luminescent metal-organic frameworks (MOFs) have recently received great attention due to their potential applications as sensors and light-emitting devices. In these MOFs, the highly ordered fluorescent organic linkers positioning prevents excited-state self-quenching and rotational motion, enhancing their light-harvesting properties. Here, the exciton migration between the organic linkers with the same chemical structure but different protonation degrees in Zr-based MOFs was explored and deciphered using ultrafast laser spectroscopy and density functional theory calculations. First, we clearly demonstrate how hydrogen-bonding interactions between free linkers and solvents affect the twisting changes, internal conversion processes, and luminescent behavior of a benzoimidazole-based linker. Second, we provide clear evidence of an ultrafast energy transfer between well-aligned adjacent linkers with different protonation states inside the MOF. These findings provide a new fundamental photophysical insight into the exciton migration dynamics between linkers with different protonation states coexisting at different locations in MOFs and serve as a benchmark for improving light-harvesting MOF architectures.
UR - http://hdl.handle.net/10754/669251
UR - https://pubs.acs.org/doi/10.1021/acs.jpclett.1c01053
U2 - 10.1021/acs.jpclett.1c01053
DO - 10.1021/acs.jpclett.1c01053
M3 - Article
C2 - 34008983
SN - 1948-7185
SP - 4917
EP - 4927
JO - The Journal of Physical Chemistry Letters
JF - The Journal of Physical Chemistry Letters
ER -