Framework-Topology-Controlled Singlet Fission in Metal–Organic Frameworks

Rajasree, Sreehari Surendran; Yu, Jierui; Fajardo-Rojas, Fernando; Fry, H. Christopher; Anderson, Ryther; Li, Xinlin; Xu, Wenqian; Duan, Jiaxin; Goswami, Subhadip; Maindan, Karan; Gómez-Gualdrón, Diego A.; Deria, Pravas

doi:10.1021/jacs.3c03918

Framework-Topology-Controlled Singlet Fission in Metal–Organic Frameworks

Journal Article · Tue Aug 01 04:00:00 EDT 2023 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.3c03918· OSTI ID:2404918

Rajasree, Sreehari Surendran ^[1]; Yu, Jierui ^[1]; ^[2]; ^[3]; Anderson, Ryther ^[2]; ^[1]; Xu, Wenqian ^[4]; Duan, Jiaxin ^[5]; ^[5]; Maindan, Karan ^[1]; Gómez-Gualdrón, Diego A. ^[2]; ^[1]

Southern Illinois Univ., Carbondale, IL (United States)
Colorado School of Mines, Golden, CO (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States). Center for Nanoscale Materials (CNM)
Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Northwestern Univ., Evanston, IL (United States)

Singlet fission (SF) has been explored as a viable route to improve photovoltaic performance by producing more excitons. Efficient SF is achieved through a high degree of interchromophoric coupling that facilitates electron super exchange to generate triplet pairs. However, strongly coupled chromophores often form excimers that can serve as an SF intermediate or a low-energy trap site. The succeeding decoherence process, however, requires an optimum electronic coupling to facilitate the isolation of triplet production from the initially prepared correlated triplet pair. Conformational flexibility and dielectric modulation can provide a means to tune the SF mechanism and efficiency by modulating the interchromophoric electronic interaction. Such a strategy cannot be easily adopted in densely stacked traditional organic solids. Here, we show that the assembly of the SF-active chromophores around well-defined pores of solution-stable metal-organic frameworks (MOFs) can be a great platform for a modular SF process. A series of three new MOFs, built out from 9,10-bis(ethynylenephenyl)anthracene-derived struts, show a topology-defined packing density and conformational flexibility of the anthracene core to dictate the SF mechanism. Various steady-state and transient spectroscopic data suggest that the initially prepared singlet population can prefer either an excimer-mediated SF or a direct SF (both through a virtual charge-transfer (CT) state). Finally, these solution-stable frameworks offer the tunability of the dielectric environment to facilitate the SF process by stabilizing the CT state. Given that MOFs are a great platform for various photophysical and photochemical developments, generating a large population of long-lived triplets can expand their utilities in various photon energy conversion schemes.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-06CH11357; FG02-87ER13808

OSTI ID:: 2404918

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 32 Vol. 145; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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