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AbstractA combined experimental and computational study of the dinuclear rhenium(V) complex containing (ReO)2(µ-O) core is presented in this article. The solid-state [Re2Cl4(O)2(µ-O)(3,5-lut)4] (3,5-lut = 3,5-dimethylpyridine) complex was characterised structurally (by single crystal X-ray diffraction) and spectroscopically (by IR, NMR, UV-VIS). The electronic structure was examined using the density functional theory (DFT) method. The spin-allowed electronic transitions were calculated using the time-dependent DFT method, and the UV-VIS spectrum was discussed.