3D Electron Diffraction Structure Determination of Terrylene, a Promising Candidate for Intermolecular Singlet Fission

Abstract

Herein we demonstrate the prowess of the 3D electron diffraction approach by unveiling the structure of terrylene, the third member in the series of peri‐condensed naphthalene analogues, which has eluded structure determination for 65 years. The structure was determined by direct methods using electron diffraction data and corroborated by dispersion‐inclusive density functional theory optimizations. Terrylene crystalizes in the monoclinic space group P21/a, arranging in a sandwich‐herringbone packing motif, similar to analogous compounds. Having solved the crystal structure, we use many‐body perturbation theory to evaluate the excited‐state properties of terrylene in the solid‐state. We find that terrylene is a promising candidate for intermolecular singlet fission, comparable to tetracene and rubrene.

True molecular conformation and structure determination by three-dimensional electron diffraction of PAH by-products potentially useful for electronic applications

“…7(a) and 7(b)). The intermolecular distance is about 3.5 A ˚, similar to that observed in terrylene, another PAH recently solved by the 3D ED method and potentially promising for electronic applications (Hall et al, 2021).…”

“…The degree of singlet exciton charge-transfer character (%CT) was calculated by double-Bader analysis (DBA) (Wang et al, 2018;Liu et al, 2020c). The results for rubrene and pentacene are from Wang et al (2016), the results for quaterrylene, perylene and tetracene are from Wang et al (2018), the results for anthracene are from Liu et al (2020c), and the results for terrylene are from Hall et al (2021).…”

Electron Diffraction of 3D Molecular Crystals

“…In a field continually grappling with the myriad pitfalls associated with analysis of complex 2D NMR spectra, the clarity provided by a corroborating crystal structure seems almost cathartic. Furthermore, when applied in tandem with comparative genomics or metabolomics (to mine relevant biosynthetic gene clusters) and synthetic biology (to express those genes in model organisms), 3D ED could also significantly accelerate the rate of NP discovery. − More broadly, 3D ED is rapidly finding a complementary niche within the wider context of synthetic chemistry; a growing number of reports now feature 3D ED structures of relevant synthetic targets or intermediates which proved unsuitable for single-crystal XRD. − These structures include two noncanonical amino acids bearing all-carbon quaternary stereocenters, a trio of organic semiconductors solved at ultrahigh resolution (one of which is depicted in Figure E), a family of electron-deficient expanded helicenes, a pentacyclic indole-derived ester, and a synthetic mimic of the cuboidal subunit in the oxygen-evolving complex of photosystem II …”

3Delectron diffraction for structure determination of small‐molecule nanocrystals: A possible breakthrough for the pharmaceutical industry

“…Recently, 3D ED has also been applied to the structure determination of complex polyaromatic hydrocarbons (PAHs). The crystal structure of terrylene was determined by direct methods (Hall et al, 2021), an achievement that could not be perform by single crystal X‐ray diffraction due to limited crystal size and the thin leaflet morphology (Figure 6c). Terrylene has found many uses in pigments, dyes, and small‐molecule organic devices (Weil et al, 2010), in particular, it is a very capable fluorophore, potentially usable as label for single molecule spectroscopy (Białkowska et al, 2017).…”