Charge Transfer Complexes of 1,3,6-Trinitro-9,10-phenanthrenequinone with Polycyclic Aromatic Compounds.

Roman Linko,Pavel Dorovatovskii,Michael Ryabov,Pavel Strashnov,Victor Davydov,Victor Khrustalev

doi:10.3390/molecules26216391

Abstract

Understanding the interactions of organic donor and acceptor molecules in binary associates is crucial for design and control of their functions. Herein, we carried out a theoretical study on the properties of charge transfer complexes of 1,3,6-trinitro-9,10-phenanthrenequinone (PQ) with 23 aromatic π-electron donors. Density functional theory (DFT) was employed to obtain geometries, frontier orbital energy levels and amounts of charge transfer in the ground and first excited states. For the most effective donors, namely, dibenzotetrathiafulvalene, pentacene, tetrathiafulvalene, 5,10-dimethylphenazine, and tetramethyl-p-phenylenediamine, the amount of charge transfer in the ground state was shown to be 0.134−0.240 e−. Further, a novel charge transfer complex of PQ with anthracene was isolated in crystalline form and its molecular and crystal structure elucidated by single-crystal synchrotron X-ray diffraction.

Highlights

The degree of electron transfer in charge transfer complexes (CTCs) is governed by the difference between the donor ionization potential and the acceptor electron affinity which can be approximated as the difference between the donor highest occupied molecular orbital (HOMO) and the acceptor lowest unoccupied molecular orbital (LUMO) [1]
The same goes for ∆CTC EMO : the HOMO–LUMO energy difference in CTCs decreases from 3.10 eV to 1.37 eV for complexes of PQ with benzene and pentacene, respectively
In this study we explored a series of 23 charge transfer complexes based on 1,3,6trinitro-9,10-phenanthrenequinone and different electron donors by means of density functional theory

Summary

Introduction

Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations. Organic π-π charge transfer complexes (CTCs) form a special class of binary compounds stabilized by partial electron transfer between noncovalently interacting donor (D). The degree of electron transfer in CTCs is governed by the difference between the donor ionization potential and the acceptor electron affinity which can be approximated as the difference between the donor highest occupied molecular orbital (HOMO) and the acceptor lowest unoccupied molecular orbital (LUMO) [1]. The. HOMO-LUMO energy gap can be obtained from DFT calculations

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Results

Conclusion