Wavelength-Dependent Excitonic Properties of Covalent Organic Frameworks Explored by Theory and Experiments

Streater, Daniel; Hu, Wenhui; Kelley, Matthew S.; Yang, Sizhuo; Kohlstedt, Kevin L.; Huang, Jier

doi:10.1021/acs.jpcc.3c02296

Wavelength-Dependent Excitonic Properties of Covalent Organic Frameworks Explored by Theory and Experiments

Journal Article · Thu Jun 15 00:00:00 EDT 2023 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.3c02296· OSTI ID:1996974

Streater, Daniel ^[1]; Hu, Wenhui ^[2]; Kelley, Matthew S. ^[3]; Yang, Sizhuo ^[2]; ^[3]; ^[4]

Marquette University, Milwaukee, WI (United States); Boston College
Marquette University, Milwaukee, WI (United States)
Northwestern University, Evanston, IL (United States)
Marquette University, Milwaukee, WI (United States); Boston College, Chestnut Hill, MA (United States)

Many aspects of the correlation between physical structure, light harvesting, and excitonic properties of covalent organic frameworks (COFs) remain unclear despite being key properties determining their photocatalytic function. One area of COF research that could bring clarity is through using both electronic structure theory and time-resolved spectroscopic analysis over a series of isomeric COFs. Here, we show structure-property relationships between four imine COFs built from a combination of ditopic and tritopic monomers using transient absorption spectroscopy together with time-dependent density functional theory. We find that monomer selection only moderately affects the charge transfer (CT) behavior of the COFs. Instead, we infer that imine chemistry profoundly impacts CT by acting as a CT mediator. Moreover, we discover two distinct valence bands arising from varying degrees of locally excited/CT mixing, which is responsible for energy dependent exciton dynamics. Finally, we use theory to hypothesize that interlayer interactions can modify excitonic properties that we correlate with tail states commonly observed, but rarely investigated in COFs. Furthermore, these results reveal that imine chemistry should be recognized as a very important factor to consider in the development of COF photocatalysts and the correlation of their structural environment with light harvesting and CT properties that should ultimately determine their photocatalytic function.

View Accepted Manuscript (DOE)

Research Organization:: Boston College, Chestnut Hill, MA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: SC0020122

OSTI ID:: 1996974

Alternate ID(s):: OSTI ID: 2335691

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 25 Vol. 127; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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