Michael J. Ferry

Excited-state absorption of a bipyridyl platinum(II) complex with alkynyl-benzothiazolylfluorene units

The singlet excited-state lifetime of a bipyridyl platinum(II) complex containing two alkynyl-benzothiazolylfluorene units was determined to be 145+/-105 ps by fitting femtosecond transient difference absorption data, and the triplet quantum yield was measured to be 0.14. A ground-state absorption cross section of 6.1 x 10(-19) cm(2) at 532 nm was deduced from UV-visible absorption data. Excited-state absorption cross sections of (6.7+/-0.1) x 10(-17) cm(2) (singlet) and (4.6+/-0.1) x 10(-16) cm(2) (triplet) were obtained by using a five-level dynamic model to fit open-aperture Z scans at picosecond and nanosecond pulse widths and a variety of pulse energies. For this complex, the ratio of the triplet excited-state absorption cross section to the ground-state absorption cross section--long used as a figure of merit for reverse saturable absorbers--thus stands at 754, to our knowledge the largest ever reported at 532 nm wavelength.

Excited-state absorption in a terpyridyl platinum(II) pentynyl complex.

The singlet excited-state lifetime of a terpyridyl platinum(II) pentynyl complex was determined to be 268+/-87 ps by fitting femtosecond transient absorption data, the triplet excited-state lifetime was found to be 62 ns by fitting nanosecond transient absorption decay data, and the triplet quantum yield was measured to be 0.16. A ground-state absorption cross section of 2.5 x 10(-19) cm(2) at 532 nm was deduced from UV-vis absorption data. Excited-state absorption cross sections of 3.5 x 10(-17) cm(2) (singlet) and 4.5 x 10(-17) cm(2) (triplet) were obtained by using a five-level dynamic model to fit open-aperture Z scans at picosecond and nanosecond pulse widths and a variety of pulse energies.

Spectroscopic properties of Co2+ in related spinels

We report the absorption and fluorescence spectra of divalent cobalt (Co2+) in a series of related spinels Mg(1−x)CoxAlBOC, where B=2, 4, 6, C=4, 7, 10, and x represents the amount of Co2+ that substitutes for Mg2+ in tetrahedral sites of Td symmetry. The spectra support the assumption that both Mg2+ and Co2+ prefer the tetrahedral cation sites during the growth of these crystalline materials. These observations also support earlier conclusions obtained from crystallographic and thermodynamic studies of the MgO and Al2O3 phase diagram. The observed spectra are analyzed and compared to calculated electronic levels derived from lattice-sum models using crystallographic data determined from the crystals grown in the present studies. Comments are made in relevance to the use of these crystals as saturable absorbers for near infrared Q-switched lasers.

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 complexs 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.

Poling of visible chromophores in millimeter-thick PMMA host

We report the direct high-voltage poling of the chromophores 4-methoxy-4’-nitrostilbene (MNS) and 2-methyl-4-nitroaniline (MNA) in a 1.2 mm thick polymethylmethacrylate (PMMA) host. The DC fields used to pole the guest-host system varied in strength from 58 to 67 Vμm−1, and the presence of chromophore orientation in the poled samples was subsequently analyzed via Maker fringe analysis. We observed values of the SHG coefficient d33 of 0.7 to 1.75pm/V at 532nm.

Reverse saturable absorption (RSA) in fluorinated iridium derivatives

The photophysical properties of cyclometallated iridium compounds are beneficial for nonlinear optical (NLO) applications, such as the design of reverse saturable absorption (RSA) materials. We report on the NLO characterization of a family of compounds of the form [Ir(pbt)2(LX)], where pbt is 2-phenylbenzothiazole and LX is a beta-diketonate ligand. In particular, we investigate the effects of trifluoromethylation on compound solubility and photophysics compared to the parent acetylacetonate (acac) version. The NLO properties, such as the singlet and triplet excited-state cross sections, of these compounds were measured using the Z-scan technique. The excited-state lifetimes were determined from visible transient absorption spectroscopy.

Fluence-induced reversal of saturable absorption in a ruthenium-based porphyrin

Experimental nonlinear absorption data obtained using the open-aperture Z-scan technique are presented for 2, 3, 7, 8, 12, 17, 18-octaethyl-21H, 23H-porphine ruthenium (II) carbonyl in tetrahydrofuran. These data show saturation of nonlinear absorption dominating at low fluence but being overcome by induced absorption (reverse saturable absorption) at high fluence. Large-angle scattering measurements demonstrate that the induced absorption is real and not merely the result of scattering of light outside of the collection aperture of the detector by scattering centers induced at high fluence. A possible mechanism based on a four-band effective rate equation model is proposed. The model is used to accurately predict the results of Z scans taken at different pulse energies and to extract values for excited-state lifetimes and absorption cross sections from the experimental data.

Tricycloquinazoline-based organometallic compounds for optical switching

The nonlinear absorption was studied for compounds linking tricycloquinazoline to a number of iridium groups. It was determined that the excited-state cross section was highest for the compound with a single iridium group.

Characterization of the nonlinear optical properties of a photodegradation-resistant dye/solvent system

Experimental measurements were performed to completely characterize the linear and nonlinear optical properties in butyl salicylate solution of a novel bipyridyl platinum(II) complex bearing benzothiazolylethynylfluorene ligands. This paper describes the analysis of the resulting experimental data and reports the values of the ground- and excited-state absorption cross sections and of the other photophysical parameters characterizing the chromophore/solvent system.

Engineering the ground- and excited-state absorption spectra of broadband reverse saturable absorbers

We exploit the strong spin-orbit coupling in iridium to modify the linear absorption spectrum of a novel iridium(III) complex so as to broaden the spectral region over which it exhibits reverse saturable absorption. We discuss the design of the new chromophore, present its ground-state absorption spectrum, and report values of its singlet excited-state lifetime and singlet and triplet excited-state absorption cross sections, determined from femtosecond transient difference absorption measurements and nanosecond and picosecond open-aperture Z scans.