Tunable Emission of Iridium(III) Complexes Bearing Sulfur-Bridged Dipyridyl Ligands.

A series of six new cyclometalated iridium(III) complexes [Ir(ppy)2(N∧N)][PF6] (ppy = 2-phenylpyridine) is reported herein. Proligands bis(pyridin-2-yl)sulfane (1a), 2,2'-sulfinyldipyridine (1b), 2,2'-sulfonyldipyridine (1c), bis(4-methylpyridin-2-yl)sulfane (2a), 2,2'-sulfinylbis(4-methylpyridine) (2b), and 2,2'-sulfonylbis(4-methylpyridine) (2c) were synthesized, characterized, and employed as the N∧N ancillary ligand. Changing the oxidation state of the sulfur atom serves as a switch to alter the emissive state from that of mainly 3LC character (blue-green emission) to one of 3MLCT/3LLCT character (yellow emission). Sulfide and sulfoxide complexes Ir(1a), Ir(1b), Ir(2a), and Ir(2b) show identical, vibrationally structured emission profiles with maxima at 478, 510, 548 nm in CH2Cl2 solutions resulting from a 3LC state. In contrast, sulfone complexes Ir(1c) and Ir(2c) show broad, red-shifted 3CT emission (552 and 537 nm, respectively).