The photophysical properties of the complex (L)Ir(ppy)(2)(+), where ppy = 2-phenylpyridine and L) 4,4'-(2,2'-bipyridine-5,5'-diylbis(ethyne-2,1-diyl))bis(N,N-dihexylaniline), have been investigated under one- and two-photon excitation conditions. In THF solution, the complex exhibits broad ground-state absorption with lambda(max) approximate to 500 nm and weak photoluminescence with lambda(max) approximate to 730 nm. Excitation of (L) Ir(ppy)(2)(+) at 355 nm produces a long-lived excited state (tau approximate to 1 As) that features a strong excited-state absorption in the near-infrared (lambda(max) approximate to 875 nm, Delta is an element of approximate to 6.1 x 10(4) M-1 cm(-1)). Photoluminescence and transient absorption studies of (L) Ir(ppy)(2)(+) carried out using 5ns, 1064 nm pulsed excitation demonstrate that the same long-lived and strongly absorbing excited state can be efficiently produced by two-photon absorption. Solutions of the complex in THF display nonlinear absorption of 5 ns, 1064 nm pulses in a process that is believed to involve a combination of two-photon absorption and reverse saturable absorption.