A series of cationic heteroleptic iridium(III) complexes bearing tris-diimine ligands [Ir(phen)2(R-phen)]3+ (R-phen = phenanthroline (1), 3,8-diphenylphenanthroline (2), 3,8-dipyrenylphenanthroline (3), 3-phenylphenanthroline (4), 3-pyrenylphenanthroline (5), and 3,8-diphenylethynylphenanthroline (6)) were synthesized and characterized. These complexes possessed phen ligand-localized 1π,π* transitions below 300 nm, and charge transfer (1CT) and/or 1π,π* transitions between 300 and 520 nm. In 1, 2, 4, and 6, the low-energy bands were mixed 1CT/1π,π*. However, the increased π-donating ability of the pyrenyl substituent(s) in 3 and 5 split the low-energy bands into a pyrene-based 1π,π* transition at 300-380 nm and an intraligand charge transfer (1ILCT) transition at 380-520 nm. All complexes were emissive at room temperature in CH3CN, but the parentage of the emitting state varied depending on the R substituent(s). Complex 1 exhibited predominantly phen ligand-localized 3π,π* emission mixed with metal-to-ligand charge transfer (3MLCT) character, whereas the emission of 2, 4, and 6 was predominantly from the excited-state with 3π,π*/3ILCT/3MLCT character. The emission from 3 and 5 was dominated by pyrene-based 3π,π* states mixed with 3ILCT character. The different natures of the lowest triplet excited states were also reflected by the different spectral features and lifetimes of the triplet transient absorption of these complexes. Complexes 3 and 5 had singlet oxygen quantum yields as high as 81 and 72%, respectively. Both gave submicromolar phototoxicities toward cancer cells (SK-MEL-28 human melanoma) and bacteria ( S. aureus and S. mutans) with visible-light activation (and marginal to no photobiological activity with red light). Their visible-light phototherapeutic indices (PIs) toward SK-MEL-28 cells were 248 for 3 and >435 for 5; PIs were lower in bacteria (≤62) because of their inherent antimicrobial activities. Both complexes were shown to produce substantial amounts of intracellular reactive oxygen species (ROS), which may account for their photobiological activities.

Modulation instability, breather formation, and the Fermi–Pasta–Ulam–Tsingou recurrence (FPUT) phenomena are studied in this article. Physically, such nonlinear systems arise when the medium is slightly anisotropic, e.g., optical fibers with weak birefringence where the slowly varying pulse envelopes are governed by these coherently coupled Schrödinger equations. The Darboux transformation is used to calculate a class of breathers where the carrier envelope depends on the transverse coordinate of the Schrödinger equations. A “cascading mechanism” is utilized to elucidate the initial stages of FPUT. More precisely, higher order nonlinear terms that are exponentially small initially can grow rapidly. A breather is formed when the linear mode and higher order ones attain roughly the same magnitude. The conditions for generating various breathers and connections with modulation instability are elucidated. The growth phase then subsides and the cycle is repeated, leading to FPUT. Unequal initial conditions for the two waveguides produce symmetry breaking, with “eye-shaped” breathers in one waveguide and “four-petal” modes in the other. An analytical formula for the time or distance of breather formation for a two-waveguide system is proposed, based on the disturbance amplitude and instability growth rate. Excellent agreement with numerical simulations is achieved. Furthermore, the roles of modulation instability for FPUT are elucidated with illustrative case studies. In particular, depending on whether the second harmonic falls within the unstable band, FPUT patterns with one single or two distinct wavelength(s) are observed. For applications to temporal optical waveguides, the present formulation can predict the distance along a weakly birefringent fiber needed to observe FPUT.