Manipulating triplet states: tuning energies, absorption, lifetimes, and annihilation rates in anthanthrene derivatives.

The photophysical properties of anthanthrene, four anthanthrene derivatives containing varying phenyl and p-tBu-phenyl substituents, and two anthanthrones with phenyl and p-tBu-phenyl substituents are examined. In general, as the anthanthrenes and anthanthrones become more substituted, red-shifts are observed in the peak maxima of the ground- and excited-state absorption and fluorescence spectra. The anthanthrones have large (>0.8) intersystem crossing (ISC) quantum yields (ΦT) likely caused by nπ* character in the ground or excited states. A bromo-substituted anthanthrene has a unity ISC yield due to an ISC rate constant of 2.5 × 1010 s-1 caused by heavy-atom induced, spin-orbit coupling. This leads to low fluorescence quantum yields (ΦF) in these three derivatives. The parent anthanthrene and remaining derivatives behave much differently. All have ΦF values from 0.58-0.84 with lower ΦT values as radiative decay outcompetes ISC. The anthanthrones have remarkable excited-state absorption with strong, broad transitions across the visible region with weaker transitions extending to nearly two µm. The anthanthrenes have very similar-shaped, broad transitions in the visible which can be shifted ∼60 nm by controlling the substituents. The triplet lifetimes range from 31-1200 µs and increase as the ISC yields decrease; the bromo-substituted anthanthrene is the shortest, followed by the anthanthrones then the other anthanthrenes. The rate of triplet-triplet annihilation is also affected by the presence of substituents; as the amount of steric bulk is increased, the rate of annihilation decreases.

Photodriven Oxygen Removal via Chromophore-Mediated Singlet Oxygen Sensitization and Chemical Capture.

We report a general, photochemical method for the rapid deoxygenation of organic solvents and aqueous solutions via visible light excitation of transition metal chromophores (TMCs) in the presence of singlet oxygen scavenging substrates. Either 2,5-dimethylfuran or an amino acid (histidine or tryptophan methyl ester) was used as the substrate in conjunction with an iridium or ruthenium TMC in toluene, acetonitrile, or water. This behavior is described for solutions with chromophore concentrations that are pertinent for both luminescence and transient absorption spectroscopies. These results consistently produce TMC lifetimes comparable to those measured using traditional inert gas sparging and freeze-pump-thaw techniques. This method has the added benefits of providing long-term stability (days to months); economical preparation due to use of inexpensive, commercially available oxygen scrubbing substrates; and negligible size and weight footprints compared to traditional methods. Furthermore, attainment of dissolved [O2] < 50 µM makes this method relevant to any solution application requiring low dissolved oxygen concentration in solution, provided that the oxygenated substrate does not interfere with the intended chemical process.

Nonlinear optical characterization of multinuclear iridium compounds containing tricycloquinazoline.

Nonlinear optical properties were characterized for a series of multinuclear iridium compounds of the form TCQ[IrIII(ppz)2]n, where n=1, 2, or 3, TCQ is tricycloquinazoline, and ppz is 1-phenylpyrazole. Transient absorption (TA) spectroscopy indicated that the triplet metal-to-ligand charge transfer excited state was formed on a subpicosecond time scale and decayed back to the ground state on a microsecond time scale, consistent with precedents in the literature. TA bands were observed for all three compounds from 475 to 900 nm, implying the potential for reverse-saturable absorption (RSA) at those wavelengths. Z-scan measurements using picosecond and nanosecond pulses were obtained at 532 nm and confirmed the presence of RSA behavior for all three compounds. The triplet excited state cross sections and the RSA figure of merit were found to decrease with increasing n:1>2∼3.

Strong triplet excited-state absorption in a phenanthrolinyl iridium(III) complex with benzothiazolylfluorenyl-substituted ligands.

Femtosecond transient difference absorption (fs TA) measurements, together with a series of open-aperture Z scans at picosecond and nanosecond pulse widths and a variety of pulse energies, were performed on a 1,10-phenanthrolinyl iridium(III) complex bearing ligands containing a benzothiazolylfluorenyl motif. An analysis of decay data from the fs TA experiment yields a value of 1.24±0.26 ns for the singlet excited-state lifetime τ(S) of the complex. By fitting the Z scans to a five-level dynamic model incorporating the independently measured value of τ(S) and previously reported values of the complex's triplet quantum yield (0.13) and triplet excited-state lifetime (230 ns), we obtain values of 3.5×10(-17) cm(2) (singlet) and 5.0×10(-16) cm(2) (triplet) for the excited-state absorption cross-sections of the complex in toluene solution at 532 nm; the latter value represents one of the largest triplet excited-state absorption cross-sections ever reported at this wavelength. The ratio of the triplet excited-state cross-section to the ground-state absorption cross-section exceeds 3800.