Issue 40, 2023

Comparing the structures and photophysical properties of two charge transfer co-crystals

Abstract

Organic co-crystals have emerged as a promising class of semiconductors for next-generation optoelectronic devices due to their unique photophysical properties. This paper presents a joint experimental-theoretical study comparing the crystal structure, spectroscopy, and electronic structure of two charge transfer co-crystals. Reported herein is a novel co-crystal Npe:TCNQ, formed from 4-(1-naphthylvinyl)pyridine (Npe) and 7,7,8,8-tetracyanoquinodimethane (TCNQ) via molecular self-assembly. This work also presents a revised study of the co-crystal composed of Npe and 1,2,4,5-tetracyanobenzene (TCNB) molecules, Npe:TCNB, herein reported with a higher-symmetry (monoclinic) crystal structure than previously published. Npe:TCNB and Npe:TCNQ dimer clusters are used as theoretical model systems for the co-crystals; the geometries of the dimers are compared to geometries of the extended solids, which are computed with periodic boundary conditions density functional theory. UV-Vis absorption spectra of the dimers are computed with time-dependent density functional theory and compared to experimental UV-Vis diffuse reflectance spectra. Both Npe:TCNB and Npe:TCNQ are found to exhibit neutral character in the S0 state and ionic character in the S1 state. The high degree of charge transfer in the S1 state of both Npe:TCNB and Npe:TCNQ is rationalized by analyzing the changes in orbital localization associated with the S1 transitions.

Graphical abstract: Comparing the structures and photophysical properties of two charge transfer co-crystals

Supplementary files

Article information

Article type
Paper
Submitted
03 Aug 2023
Accepted
25 Sep 2023
First published
26 Sep 2023

Phys. Chem. Chem. Phys., 2023,25, 27065-27074

Author version available

Comparing the structures and photophysical properties of two charge transfer co-crystals

A. Abou Taka, J. E. Reynolds, N. C. Cole-Filipiak, M. Shivanna, C. J. Yu, P. Feng, M. D. Allendorf, K. Ramasesha, V. Stavila and L. M. McCaslin, Phys. Chem. Chem. Phys., 2023, 25, 27065 DOI: 10.1039/D3CP03720G

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