Evaluation of Through-Space Electronic Coupling in the Cofacially Aligned π-Stacked Organic Mixed-Valence System

다국어 초록 (Multilingual Abstract)

A new π-stacked compound, 1,8-bis(20,50-dimethoxy-40-methyl-[1,10-biphenyl]-4-yl)naphthalene (1) has been synthesized and characterized as a precursor molecule of monocationic mixed-valence system (MVS). Cyclic and differential pulse voltammograms reveal that the ΔE ox value between two sequential oxidation potentials is 163 mV. The three-dimensional geometries of 1, 1•+, and 12+ were obtained via using density functional theory (DFT) calculations with a range-separated hybrid functional and dispersion corrections (LC-wPBE-D3). Two dimethoxytoluene redox centers were aligned in parallel with van der Waals interplanar distances (3.50–3.70 Å). The electronic coupling in this MVS was evaluated by two different approaches: (1) Mulliken–Hush analysis of intervalence charge transfer (IVCT) band obtained from the spectroelectrochemical method, and (2) partial charge distribution analysis of quinonoidal distortion of D•+/D centers obtained from theoretical DFT calculations. The H12 were 2055 and 1903 cm−1 by (1) and (2), respectively. This work suggests that the pure through-space electronic coupling can be large when two aromatic redox centers are properly aligned.

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