Luminescent Piano-Stool Complexes Incorporating 1-(4-Cyanophenyl)imidazole: Synthesis, Spectral, and Structural Studies

Three novel luminescent piano-stool arene ruthenium complexes of general formula [(η6-arene)RuCl2(CPI)] (η6-arene = benzene, 1, p-cymene, 2, and hexamethylbenzene, 3; CPI=1-(4-cyanophenyl)imidazole were prepared.
The molecular structures of 2 and 3 were determined crystallographically. Reaction of 1−3 with EPh3 (E = P, As,
or Sb) and N−N donor bases such as 2,2‘-bipyridine and 1,10-phenanthroline afforded cationic mononuclear
complexes of general formula [(η6-arene)RuCl(CPI)(EPh3)]+ (η6-arene = C6H6, E = P (1a), E = As (1b), E = Sb
(1c); η6-arene = C10H14, E = P (2a), E = As (2b), E = Sb (2c); η6-arene = C6Me6, E = P (3a), E = As (3b),
E = Sb (3c)) and [(η6-arene)Ru(N−N)(CPI)]2+ (η6-arene = C6H6, N−N = bipy (1d), N−N = phen (1e); η6-arene
= C10H14, N−N = bipy (2d), N−N = phen (2e); η6-arene = C6Me6, N−N = bipy (3d), N−N = phen (3e)).
Molecular structures of 1a and 2a were also confirmed by X-ray crystallography. Structural studies of the complexes
2, 3, 1a, and 2a supported coordination of CPI through the imidazole nitrogen and the presence of a pendant nitrile
group. Structural data also revealed stabilization of crystal packing in the complexes 2, 3, and 2a by C−H···X (X
= Cl, F) type inter- and intramolecular interactions and in complex 1a by π−π stacking. Moreover, neutral
homonuclear bimetallic complexes 2f,g were prepared by using complex 2 as a metallo-ligand, where CPI acts as
a bridge between two metal centers. Emission spectra of the mononuclear complexes [(η6-arene)RuCl2(CPI)] and
its derivatives exhibited intense luminescence when excited in the metal to ligand charge-transfer band.