Superradiance and Directional Exciton Migration in Metal–Organic Frameworks

Rajasree, Sreehari Surendran; Yu, Jierui; Pratik, Saied Md; Li, Xinlin; Wang, Rui; Kumbhar, Amar S.; Goswami, Subhadip; Cramer, Christopher J.; Deria, Pravas

doi:10.1021/jacs.1c11979

Superradiance and Directional Exciton Migration in Metal–Organic Frameworks

Journal Article · Fri Jan 14 04:00:00 EST 2022 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.1c11979· OSTI ID:1856752

Rajasree, Sreehari Surendran ^[1]; Yu, Jierui ^[2]; ^[3]; Li, Xinlin ^[2]; ^[4]; ^[5]; ^[4]; ^[6]; ^[2]

Southern Illinois Univ., Carbondale, IL (United States); University of Minnesota
Southern Illinois Univ., Carbondale, IL (United States)
Univ. of Minnesota, Minneapolis, MN (United States)
Northwestern Univ., Evanston, IL (United States)
Univ. of North Carolina, Chapel Hill, NC (United States)
Univ. of Minnesota, Minneapolis, MN (United States); Underwriters Laboratories Inc., Northbrook, IL (United States)

Crystalline metal–organic frameworks (MOFs) are promising synthetic analogues of photosynthetic light-harvesting complexes (LHCs). The precise assembly of linkers (organic chromophores) around the topology-defined pores offers the evolution of unique photophysical behaviors that are reminiscence of LHCs. These include MOF excited states with photoabsorbed energy that is spatially dispersed over multiple linkers defining the molecular excitons. The multilinker molecular excitons display superradiance–a hallmark of coupled oscillators seen in LHCs–with radiative rate constant (k_rad) exceeding that of a single linker. Our theoretical model and experimental results on three zirconium MOFs, namely, PCN-222(Zn), NU-1000, and SIU-100, with similar topology but varying linkers suggest that the size of such molecular excitons depends on the electronic symmetry of the linker. This multilinker exciton model effectively predicts the energy transfer rate constant; corresponding single-step exciton hopping time, ranging from a few picoseconds in SIU-100 and NU-1000 to a few hundreds of picoseconds in PCN-222(Zn), matches well with the experimental data. The model also predicts the anisotropy of exciton displacement with preferential migration along the crystallographic c-axis. Overall, these findings establish various missing links defining the exciton size and dynamics in MOF-assembled linkers. Furthermore, the understandings will provide design principles, especially, positioning the catalysts or electrode relative to the linker orientation for low-density solar energy conversion systems.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Minnesota, Minneapolis, MN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0008688

OSTI ID:: 1856752

Alternate ID(s):: OSTI ID: 1847137

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 3 Vol. 144; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Superradiance and Directional Exciton Migration in Metal–Organic Frameworks

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