In 2005, Kobayashi and coworkers reported trends in the TD-DFT spectra of 17 Zn ( II ) porphyrinoids [J. Am. Chem. Soc. 2005; 127: 17697] that were analyzed using Michl's perimeter model as part of a study of the anomalous magnetic circular dichroism (MCD) spectroscopy of zinc tetraphenyltetraacenaphthoporphyrin. In recent years, it has become increasingly clear that TD-DFT calculations with the commonly used hybrid B3LYP exchange-correlation functional of the Gaussian software package are problematic in the B -band region of porphyrinoid spectra, since the degree of configurational interaction between the B and higher energy ππ* state appears to be significantly overestimated. The CAM-B3LYP functional is now often preferred for analyzing the optical properties of porphyrinoids, since it includes a long-range correction of the exchange potential, which incorporates an increasing fraction of Hartree–Fock (HF) exchange as the interelectronic separation increases, making it better suited for studying compounds where there is significant charge transfer in the electronic excited states. The trends in the TD-DFT calculations are reexamined with a wider range porphyrinoid compounds including several with pyrazino moieties and are found to provide a closer agreement with the experimental in the B -band region for complexes such as zinc tetraphenylporphyrin and phthalocyanine.
Nonlinear absorption and optical limiting properties of indium phthalocyanine (complex 1) tethered to magnetite (SiMNP-1) or silica (SiNP-1) nanoparticles have been investigated using 10 ns pulses at 532 nm laser excitation. The optical limiting behaviours of the nanocomposites and the bare phthalocyanine are compared. Investigation of the triplet state dynamics revealed highly efficient triplet state absorption in the SiMNP-1 dyad. A large nonlinear absorption (b eff ) that increased with decrease in the peak input fluence was observed for SiMNP-1. The SiNP-1 composite showed a slight increase in b eff with decreasing peak input fluence. The nonlinear optical data obtained for the SiNP-1 are within the same range of those of the indium phthalocyanine alone. The nanosecond nonlinear absorption and the optical limiting of the nanocomposites are shown to be dominated by a strong excited state absorption from a two-photon pumped state. Nonlinear scattering effects and strong excited state absorption from a two-photon pumped state account for the enhanced optical limiting behaviour of SiMNP-1 relative to the phthalocyanine alone.
The synthesis and characterization of a crown-ether-substituted 3,5-distyrylBODIPY dye with a 4-dimethylaminophenyl group at the meso-position is reported. The optical limiting properties were investigated at 532 nm, and the dye was found to have enhanced reverse saturable absorption responses during z-scan measurements. Theoretical calculations suggest that this may be due to the large dipole moment that is introduced by the benzo-fused crown ether and 4-dimethylaminophenyl substituents.
A free base porphyrin dimer bridged by a flexible amide-bonded xanthene moiety and its binuclear zinc(II) complex zinc(II) complex were synthesized and characterized. Structural characterization by MS and 1 H NMR spectroscopy confirmed the bridged porphyrin dimer structure. The properties of the dimers were characterized by IR, UV-visible absorption, fluorescence and magnetic circular dichroism (MCD) spectroscopy, and electrochemistry studies. Theoretical calculations were carried out to analyze the electronic structures of porphyrin dimers with a bridging amide-bonded xanthene moiety.
The synthesis and characterization of a crown-ether-substituted 3-styrylBODIPY dye with a 4-isopropylphenyl group at the meso-position is reported. The effect that the incorporation of Na[Formula: see text] ions into the crown ether moiety has on the photophysical properties is investigated.
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