Issue 22, 2023

Simulating excited states in metal organic frameworks: from light-absorption to photochemical CO2 reduction

Abstract

Metal–organic frameworks (MOFs) have a wide range of optoelectronic and photochemical applications, many of which are directly dependent on their excited states. Computational modelling of excited state processes could aid the rational design of effective catalysts, but simulating MOFs in their excited state is challenging. This is due to the inherent molecule/crystal duality of MOFs, their large and diverse unit cells, and the unfavourable scalability of quantum chemical methods. However, periodic and cluster models have been developed and applied to characterise the excited states of MOFs and their properties, such as charge transfer, luminescence, and photocatalytic mechanisms. Additionally, embedding techniques provide a means of explicitly incorporating the crystal environment in such models. Although many high-quality reviews have assessed computational modelling in MOFs, most have focused on the study of ground-state electronic properties. In this perspective, we focus on the computational methods available to describe the excited states of MOFs from the molecular, periodic, and embedding perspectives. To illustrate the performance of cluster and periodic models, we compare the results obtained using both approaches at different levels of theory for an exemplary MOF. We also analyse examples from modelling relevant photochemical and photophysical including charge transfer, exciton effects, chemosensing, host–guest mechanisms, thermally activated delayed fluorescence and room temperature phosphorescence. Additionally, we show how such methods can be applied to predict MOF-based photocatalytic CO2 reduction to value-added chemicals. We emphasise the advantages and limitations of current methodologies, as well as the potential for utilising databases and machine learning models in this context.

Graphical abstract: Simulating excited states in metal organic frameworks: from light-absorption to photochemical CO2 reduction

Supplementary files

Article information

Article type
Perspective
Submitted
08 avq 2023
Accepted
01 okt 2023
First published
06 okt 2023
This article is Open Access
Creative Commons BY-NC license

Mater. Adv., 2023,4, 5388-5419

Simulating excited states in metal organic frameworks: from light-absorption to photochemical CO2 reduction

M. Ingham, A. Aziz, D. Di Tommaso and R. Crespo-Otero, Mater. Adv., 2023, 4, 5388 DOI: 10.1039/D3MA00518F

This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. You can use material from this article in other publications, without requesting further permission from the RSC, provided that the correct acknowledgement is given and it is not used for commercial purposes.

To request permission to reproduce material from this article in a commercial publication, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party commercial publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements