Tuning the Ground- and Excited-State Redox Potentials of Octahedral Hexanuclear Rhenium(III) Complexes by the Combination of Terminal Halide and N-Heteroaromatic Ligands

[Image: see text] The present study reports that the ground- and excited-state Re(6)(23e)/Re(6)(24e) redox potentials of an octahedral hexanuclear rhenium(III) complex can be controlled by systematically changing the number and type of the N-heteroaromatic ligand (L) and the number of chloride ions at the six terminal positions. Photoirradiation of [Re(6)(μ(3)-S)(8)Cl(6)](4–) with an excess amount of L afforded a mono-L-substituted hexanuclear rhenium(III) complex, [Re(6)(μ(3)-S)(8)Cl(5)(L)](3–) (L = 4-dimethylaminopyridine (dmap), 3,5-lutidine (lut), 4-methylpyridine (mpy), pyridine (py), 4,4′-bipyridine (bpy), 4-cyanopyridine (cpy), and pyrazine (pz)). The bis- and tris-lut-substituted complexes, trans- and cis-[Re(6)(μ(3)-S)(8)Cl(4)(lut)(2)](2–) and mer-[Re(6)(μ(3)-S)(8)Cl(3)(lut)(3)](−), were synthesized by the reaction of [Re(6)(μ(3)-S)(8)Cl(6)](3–) with an excess amount of lut in refluxed N,N-dimethylformamide. The mono-L-substituted complexes showed one-electron redox processes assignable to E(1/2)[Re(6)(23e)/Re(6)(24e)] = 0.49–0.58 V versus Ag/AgCl. The ground-state oxidation potentials were linearly correlated with the pK(a) of the N-heteroaromatic ligand [pK(a)(L)], the (1)H NMR chemical shift of the ortho proton on the coordinating ligand, and the Hammett constant (σ) of the pyridyl-ligand substituent. The series of [Re(6)(μ(3)-S)(8)X(6–n)(L)(n)](n−4) complexes (n = 0, X = Cl, Br, I, or NCS; n = 1–3, X = Cl) showed a linear correlation with the sum of the Lever electrochemical parameters at the six terminal ligands (ΣE(L)). The cyclic voltammograms of the mono-L-substituted complexes (L = bpy, cpy, and pz) showed one-electron redox waves assignable to E(1/2)(L(0)/L(–)) = −1.28 to −1.48 V versus Ag/AgCl. Two types of photoluminescences were observed for the complexes, originating from the cluster core-centered excited triplet state ((3)CC) for L = dmap, lut, mpy, and py and from the metal-to-ligand charge-transfer excited triplet state ((3)MLCT) for L = bpy, cpy, and pz. The complexes with the (3)CC character exhibited emission features and photophysical properties similar to those of ordinary hexanuclear rhenium complexes. The emission maximum wavelength of the complexes with (3)MLCT shifted to the longer wavelength in the order L = 4-phenylpyridine (ppy), bpy, pz, and cpy, which agreed with the difference between E(1/2)[Re(6)(23e)/Re(6)(24e)] and E(1/2)(L(0)/L(–)). The calculated oxidation potential of the excited hexanuclear rhenium complex with the (3)CC character was linearly correlated with pK(a)(L), σ, and ΣE(L). The ground- and excited-state oxidation potentials were finely tuned by the combination of halide and L ligands at the terminal positions.