A series of eight new octahedral rhenium cluster complexes with the general formula trans-[{Re6Q8}L4X2] (Q = S or Se; L = 1,2-Bis(4-pyridyl)ethylene (bpe) or 1,3-Bis(4-pyridyl)propane (bpp); X = Cl or Br) was synthesized and investigated. While bpe is a ligand with a conjugated aromatic system, bpp represents a molecule of opposite type and has independent aromatic systems of the two pyridine rings. It was shown that this difference in the electronic structure of the ligands has a fundamental effect on the electronic structure, electrochemical and luminescent properties of the corresponding cluster complexes. Specifically, the [{Re6Q8}(bpe)4X2] complexes in solutions show multiple quasi-reversible electrochemical transitions associated with reduction of the organic ligands. At the same time, the trans-[{Re6Q8}(bpp)4X2] complexes show multielectron quasi-irreversible reduction processes, which correlate with the mixed character of the lowest unoccupied molecular orbitals of these complexes. All the obtained new compounds exhibit red photoluminescence. The photophysical parameters (emission lifetimes and quantum yields) measured for the bpp complexes exceed those revealed for bpe complexes by more than an order of magnitude.
Keywords: DFT calculations; cluster; electrochemistry; luminescence; pyridine ligand; rhenium.