Emission Quenching in Tetraphenylfuran Crystal: Why This Propeller-Shaped Molecule Does Not Emit in the Condensed Phase

Due to their substantial fluorescence quantum yields in the crystalline phase, propeller-shaped molecules have recently gained significant attention as potential emissive materials for optoelectronic applications. For the family of cyclopentadiene derivatives, light-emission is highly dependent on the nature of heteroatomic substitutions. In this paper, we investigate excited state relaxation pathways in the tetraphenyl-furan molecule (TPF), which in contrast with other molecules in the family, shows emission quenching in the solid-state. For the singlet manifold, our calculations show nonradiative pathways associated with C-O elongation are blocked in both vacuum and the solid state. A fraction of the population can be transferred to the triplet manifold and, subsequently, to the ground state in both phases. This process is expected to be relatively slow due to the small spin-orbit couplings between the relevant singlet-triplet states. Emission quenching in crystalline TPF seems to be in line with more efficient exciton hopping rates. Our simulations help clarify the role of conical intersections, population of the triplet states and crystalline structure in the emissive response of propeller-shaped molecules

Excited state mechanisms in crystalline carbazole: the role of aggregation and isomeric defects

The molecule of Carbazole (Cz) is commonly used as a building block in organic materials for optoelectronic applications, acting as light-absorbing, electron donor and emitting moiety. Crystals from Cz and derivatives display ultralong phosphorescence at room temperature. However, different groups have reported inconsistent quantum efficiencies for the same compounds. In a recent experimental study by Liu et al (Nature Materials 2021, 20, 175-180), the ultralong phosphoresce properties of Cz has been associated with the presence of small fractions of isomeric impurities from commercially available Cz. In this paper, we use state-of-the-art computational approaches to investigate light-induced processes in crystalline and doped Cz. We revisited the role of aggregation and isomeric impurities on the excited state pathways and analyse the mechanisms for exciton, Dexter energy transfer and electron transport based on Marcus and Marcus-Levich-Jortner theories. Our excited state mechanisms provide a plausible interpretation for the experimental results and support the formation of charge-separated states at the defect/Cz molecular interface. These results contribute to a better understanding of the factors enhancing the excited state lifetimes in organic materials and the role of doping with organic molecules

Stepwise double excited-state proton transfer is not possible in 7-azaindole dimer

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.MB and NK would like to thank the support from the Deutscher Akademischer Austauschdienst (DAAD) and from the Deutsches Zentrum f¨ur Luft- und Raumfahrt (DLR) through the Thai- German mobility gran

H-Center and V-Center Defects in Hybrid Halide Perovskites

The self-trapping of holes with the formation of a molecular X2– anion is a well-established process in metal halide (MX) crystals, but V-center (2X– + h+ → X2–) and H-center (X– + Xi– + h+ → X2–) defects have not yet been confirmed in halide perovskite semiconductors. The I2– split-interstitial defect is predicted to be a spin radical in CH3NH3PbI3 with an optically excited state in the semiconductor band gap

ONIOM(QM:QM') Electrostatic Embedding Schemes for Photochemistry in Molecular Crystals.

Understanding photoinduced processes in molecular crystals is central to the design of highly emissive materials such as organic lasers and organic light-emitting diodes. The modelling of such processes is, however, hindered by the lack of excited state methodologies tailored for these systems. Embedding approaches based on the Ewald sum can be used in conjunction with excited state electronic structure methods to model the localised excitations which characterise these materials. In this article, we describe the implementation of a two-level ONIOM(QM:QM') point charge embedding approach based on the Ewald method, the Ewald Embedded Cluster (EEC) model. An alternative self-consistent method is also considered to simulate the response of the environment to the excitation. Two molecular crystals with opposing photochemical behaviour were used to benchmark the results with single reference and multireference methods. We observed that the inclusion of an explicit ground state cluster surrounding the QM region was imperative for the exploration of the excited state potential energy surfaces. Using EEC, accurate absorption and emission energies as well as S1-S0 conical intersections were obtained for both crystals. We discuss the implications of the use of these embedding schemes considering the degree of localisation of the excitation. The methods discussed herein are implemented in an open source platform (forage, https://github.com/Crespo-Otero-group/fromage) which acts as an interface between popular electronic structure codes (Gaussian, Turbomole and Molcas)

How Inter- and Intramolecular Processes Dictate Aggregation-Induced Emission in Crystals Undergoing Excited-State Proton Transfer

Aggregation-induced emission (AIE) offers a route for the development of luminescent technologies with high quantum efficiencies. Excited-state intramolecular proton transfer (ESIPT) coupled to AIE can produce devices with emission across the visible spectrum. We use a combination of theoretical models to determine the factors that mediate fluorescence in molecular crystals undergoing ESIPT. Using two materials based on 2′-hydroxychalcone as exemplar cases, we analyze how inter- and intramolecular processes determine the emissive properties in the crystal environment. This systematic investigation extends the current interpretation of AIE to polar chromophores with multiple decay pathways. We find that population of nonradiative pathways is dictated by the electronic effects of the substituents and the degree of distortion allowed in the crystal environment. Localization of the electron density is crucial to maximize fluorescence via ESIPT. Our conclusions offer design strategies for the development of luminescent molecular crystals

Role of Conical Intersections on the Efficiency of Fluorescent Organic Molecular Crystals

Organic molecular crystals are attractive materials for luminescent applications because of their promised tunability. However, the link between the chemical structure and emissive behavior is poorly understood because of the numerous interconnected factors which are at play in determining radiative and nonradiative behaviors at the solid-state level. In particular, the decay through conical intersection dominates the nonadiabatic regions of the potential energy surface, and thus, their accessibility is a telling indicator of the luminosity of the material. In this study, we investigate the radiative mechanism for five organic molecular crystals which display a solid-state emission, with a focus on the role of conical intersections in their photomechanisms. The objective is to situate the importance of the accessibility of conical intersections with regards to emissive behavior, taking into account other nonradiative decay channels, namely, vibrational decay, and exciton hopping. We begin by giving a brief overview of the structural patterns of the five systems within a larger pool of 13 crystals for a richer comparison. We observe that because of the prevalence of sheet like and herringbone packing in organic molecular crystals, the conformational diversity of crystal dimers is limited. Additionally, similarly spaced dimers have exciton coupling values of a similar order within a 50 meV interval. Next, we focus on three exemplary cases, where we disentangle the role of nonradiative decay mechanisms and show how rotational minimum energy conical intersections in vacuum lead to puckered ones in the crystal, increasing their instability upon crystallization in typical packing motifs. In contrast, molecules with puckered conical intersections in vacuum tend to conserve this trait upon crystallization, and therefore, their quantum yield of fluorescence is determined predominantly by other nonradiative decay mechanisms

Ultrafast Photoinduced Dynamics of 1,3-Cyclohexadiene Using XMS-CASPT2 Surface Hopping

A full-dimensional simulation of the photodissociation of 1,3-cyclohexadiene in the manifold of three electronic states was performed via nonadiabatic surface hopping dynamics using extended multistate complete active space second-order perturbation (XMS-CASPT2) electronic structure theory with fully analytic nonadiabatic couplings. With the 47 ± 8% product quantum yield calculated from the 136 trajectories, generally 400 fs-long, and an estimated excited lifetime of 89 ± 9 fs, our calculations provide a detailed description of the nonadiabatic deactivation mechanism, showing the existence of an extended conical intersection seam along the reaction coordinate. The nature of the preferred reaction pathways on the ground state is discussed and extensive comparison to the previously published full dimensional dynamics calculations is provided