Excited-State Characteristics of Tetracyanidonitridorhenium(V) and -technetium(V) Complexes with N‑Heteroaromatic Ligands

Six-coordinate tetracyanidonitridorhenium­(V) and -technetium­(V) with axial N-heteroaromatic ligands, (PPh<sub>4</sub>)<sub>2</sub>[MN­(CN)<sub>4</sub>L] [M = Re, L = 4-(dimethylamino)­pyridine (dmap), 3,5-lutidine (lut), 4-picoline (pic), 4-phenylpyridine (ppy), pyridine (py), 3-benzoylpyridine (3bzpy), 4,4′-bipyridine (bpy), pyrazine (pz), 4-cyanopyridine (cpy), or 4-benzoylpyridine (4bzpy); M = Tc, L = dmap, lut, pic, py, pz, or cpy] were synthesized and characterized. The crystal structures of 11 complexes were determined by single-crystal X-ray analysis. All of the complexes showed photoluminescence in the crystalline phase at room temperature. The emission maximum wavelengths (λ<sub>em</sub>) of the rhenium complexes with dmap, lut, pic, ppy, or py were similar to one another with a quite high emission quantum yield (Φ<sub>em</sub>): λ<sub>em</sub> = 539–545 nm, Φ<sub>em</sub> = 0.39–0.93, and emission lifetime (τ<sub>em</sub>) = 10–45 μs at 296 K. The emission spectra at 77 K exhibited vibronic progressions, and the emissive excited state is characterized as <sup>3</sup>[(d<sub><i>xy</i></sub>)<sup>1</sup>(d<sub>π*</sub>)<sup>1</sup>] (d<sub>π*</sub> = d<sub><i>xz</i></sub>, d<sub><i>yz</i></sub>). On the other hand, the emission maximum wavelength of the rhenium complex with 3bzpy, bpy, pz, cpy, or 4bzpy was significantly dependent on the nature of the axial ligand in the crystalline phase: λ<sub>em</sub> = 564–669 nm, Φ<sub>em</sub> ≤ 0.01–0.36, and τ<sub>em</sub> = 0.03–13.3 μs at 296 K. The emission spectra at 77 K in the crystalline phase did not show vibronic progressions. The emissive excited state of the rhenium complex with bpy, pz, cpy, or 4bzpy is assignable to originate from the metal-to-N-heteroaromatic ligand charge-transfer (MLCT)-type emission with a spin-triplet type. The change in the excited-state characteristics of rhenium complexes by the N-heteroaromatic ligand is a result of stabilization of the π* orbital of the N- heteroaromatic ligand to a lower energy level than the d<sub>π*</sub> orbitals. The emission spectral shapes of technetium complexes were almost independent of the nature of the N-heteroaromatic ligand with λ<sub>em</sub> = 574–581 nm at room temperature. The different emission characteristics between the pz and cpy coordinate rhenium complexes and the technetium analogues would be due to stabilization of technetium-centered orbitals compared with the rhenium ones in energy.