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Solvation-Enhanced Intermolecular Charge Transfer Interaction in Organic Cocrystals: Enlarged C-C Surface Close Contact in Mixed Packing between PTZ and TCNB.

ABSTRACT: The mixed π-π packing of the donor (D) and acceptor (A) molecules is the highlighting feature of the intermolecular interactions following charge transfer (CT) issues in organic cocrystal systems. There is an inverse relationship between the D-A interplanar distance and the intermolecular CT interaction. However, the D-A C-C surface close contact (relative areas) on the intermolecular CT interactions in organic cocrystal systems is rarely investigated. Herein, we designed and constructed a novel cocrystal and its solvate cocrystal. The structural and electrostatic potential analyses suggest that the solvation destroys the N-H···N hydrogen bond interaction between phenothiazine (PTZ) and 1,2,4,5-tetracyanobenzene (TCNB), which causes the TCNB molecules to have a 90° rotation along the normal axis of the PTZ plane. Thus, the D-A C-C surface close contact is enlarged, strengthening the intermolecular π-π stacking interactions and intermolecular CT interaction between PTZ and TCNB, which are further evidenced by the absorption and Raman spectroscopic analyses. This study provides rare evidence of the enlarged C-C surface close contact in the mixed packing between D and A that greatly contributes to the intermolecular CT interaction in a D-A cocrystal system. It also provides a deeper understanding of the role of solvation in the structure-property relationship of organic cocrystal materials.

SUBMITTER: Wang J

PROVIDER: S-EPMC6648522 | biostudies-literature | 2019 Jun

REPOSITORIES: biostudies-literature

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Solvation-Enhanced Intermolecular Charge Transfer Interaction in Organic Cocrystals: Enlarged C-C Surface Close Contact in Mixed Packing between PTZ and TCNB.

Wang Jing J Li Aisen A Xu Shuping S Song Chongping C Geng Yijia Y Ye Ling L Zhang Houyu H Xu Weiqing W

ACS omega 20190617 6

The mixed π-π packing of the donor (D) and acceptor (A) molecules is the highlighting feature of the intermolecular interactions following charge transfer (CT) issues in organic cocrystal systems. There is an inverse relationship between the D-A interplanar distance and the intermolecular CT interaction. However, the D-A C-C surface close contact (relative areas) on the intermolecular CT interactions in organic cocrystal systems is rarely investigated. Herein, we designed and constructed a novel ...[more]

PMID: 31460137

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Project description:In any physicochemical process in liquids, the dynamical response of the solvent to the solutes out of equilibrium plays a crucial role in the rates and products: the solvent molecules react to the changes in volume and electron density of the solutes to minimize the free energy of the solution, thus modulating the activation barriers and stabilizing (or destabilizing) intermediate states. In charge transfer (CT) processes in polar solvents, the response of the solvent always assists the formation of charge separation states by stabilizing the energy of the localized charges. A deep understanding of the solvation mechanisms and time scales is therefore essential for a correct description of any photochemical process in dense phase and for designing molecular devices based on photosensitizers with CT excited states. In the last two decades, with the advent of ultrafast time-resolved spectroscopies, microscopic models describing the relevant case of polar solvation (where both the solvent and the solute molecules have a permanent electric dipole and the mutual interaction is mainly dipole-dipole) have dramatically progressed. Regardless of the details of each model, they all assume that the effect of the electrostatic fields of the solvent molecules on the internal electronic dynamics of the solute are perturbative and that the solvent-solute coupling is mainly an electrostatic interaction between the constant permanent dipoles of the solute and the solvent molecules. This well-established picture has proven to quantitatively rationalize spectroscopic effects of environmental and electric dynamics (time-resolved Stokes shifts, inhomogeneous broadening, etc.). However, recent computational and experimental studies, including ours, have shown that further improvement is required. Indeed, in the last years we investigated several molecular complexes exhibiting photoexcited CT states, and we found that the current description of the formation and stabilization of CT states in an important group of molecules such as transition metal complexes is inaccurate. In particular, we proved that the solvent molecules are not just spectators of intramolecular electron density redistribution but significantly modulate it. Our results solicit further development of quantum mechanics computational methods to treat the solute and (at least) the closest solvent molecules including the nonperturbative treatment of the effects of local electrostatics and direct solvent-solute interactions to describe the dynamical changes of the solute excited states during the solvent response.

Dataset Information

Solvation-Enhanced Intermolecular Charge Transfer Interaction in Organic Cocrystals: Enlarged C-C Surface Close Contact in Mixed Packing between PTZ and TCNB.

Publications

Solvation-Enhanced Intermolecular Charge Transfer Interaction in Organic Cocrystals: Enlarged C-C Surface Close Contact in Mixed Packing between PTZ and TCNB.

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