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The optical limiting properties of a 1,7-dithien-3-yl-3,5-di-4-hydroxyphenyl-azaBODIPY dye and its silver nanoparticle (AgNP) conjugate on the nanosecond timescale at 532 nm are reported. The photophysicochemical properties are compared to those of the parent 1,3,5,7-tetraphenylazaBODIPY complex. The thien-3-yl rings at the distal positions facilitate conjugation to AgNPs through the Ag-S interaction and a significant red shift of the main azaBODIPY spectral band. Favorable optical limiting properties are obtained that suggest 1,3,5,7-tetraarylazaBODIPYs and their nanoparticle conjugates merit further in-depth study in this context. This is further enhanced by conjugation to AgNPs.

The valence electronic properties of some unsubstituted and peripherally substituted oxo-titanium phthalocyanines are reported. Semiempirical quantum chemical calculations show that the nature of peripheral substituents has a strong bearing on the valence electronic properties, including the state dipole moments and absorption wavelength. The non-linear optical response was measured around the the Q-band resonance. The effect of different substituents and substitution patterns on the non-linear behaviour of the samples was determined. The combined results suggest that tuning of electronic and optical properties is effectively achieved by functionalization of the edges of the conjugated ring.

The nonlinear optical (NLO) properties of lanthanide bisphthalocyanine (Lu(TBPc)Pc), including first hyperpolarizability, second hyperpolarizability and reverse saturable absorption (RSA), have been investigated. Furthermore, Lu(TBPc)Pc has also been applied for optical switch based on its RSA performance.

The usage of a modified Z-scan setup for the study of optical nonlinearities of bis-phthalocyanines is discussed. The setup leads to the selection of the pure electronic nonlinear optical response purged from other possible contributions such as molecular reorientation or thermal effects. The described experimental method is based on the capability to extract the instantaneous nonlinear response of the sample, by monitoring and managing cumulative effects and taking full advantage of the large number of probing laser pulses. This kind of approach has been applied on some sandwich-type metal bis-phthalocyanines confirming its potential for an in-depth analysis of the nonlinear response of such molecules. First results on titanium, niobium and tin bis-phthalocyanines provide information on the role of the conjugation length in their nonlinear optical response.

A novel nanoscopic composite film with alternating layers consisting of anionic octacarboxylic cobalt phthalocyanine [CoPc(COONa)₈] and cationic polyethylenimine (PEI) has been fabricated by an electrostatic, layer-by-layer, self-assembly technique. UV-vis spectroscopy revealed consecutive regular deposition of CoPc(COONa)₈/PEI onto a quartz slide. The film's delicate nanostructure was characterized by atomic force microscopy and small angle X-ray diffraction. Third-order nonlinear properties of the film performed using Z-scan measurements with 21 ps laser pulses at the incidence wavelength of 532 nm showed rather strong, nonlinear reverse saturable absorption.

Novel heteropentameric porphyrins-pyrene arrays, in which four meso-tetraphenyl porphyrins are linked to the center unit of pyrene by four acetylenyl bonds, were designed and synthesized. The newly synthesized heteropentameric compounds have been characterized by a wide range of spectroscopic methods. The third-order nonlinear optical (NLO) properties of both the metal-free and zinc compounds of the three-dimensional arrays were investigated by Z-scan experiments, showing enhanced NLO properties compared with that of the porphyrin and pyrene monomers.

Films with alternating layers containing anionic tetracarboxylic copper phthalocyanine [CuPc(COONa)₄] and cationic polydiallydimethylammonium chloride (PDDA) were fabricated by electrostatic self-assembled layer-by-layer (LBL) technique. The delicate structure of the film was characterized by a series of techniques. The third-order nonlinear optical properties of the film were measured by the Z-scan technique with laser duration of 4 ns and 21 ps at the wavelength of 532 nm. The film exhibited excellent nonlinear absorption and self-focusing effect. The second-order molecular hyperpolarizability γ value of the film was much larger than that of CuPc(COONa)₄ aqueous solution under the irradiation of whether ns or ps pulses. A series of damage experiments of the film for the intense laser pulses were conducted to prove the reliability of the experimental results under the conditions.

Two major reasons limit porphyrins photonic applications: (i) the difficulty of handling them in liquid solutions and (ii) their degradation with long exposure to light. This necessitates the use of appropriate solid matrices to host the porphyrin compounds such as Nafion (117), a stable and inert ion exchange polymer. The first part of this publication confirms such a possibility. In addition to their effective NLO properties, an enhancement of the Soret and Q-bands' absorbance width have been observed by blending three different porphyrin molecules in the Nafion column matrix membrane. This is an important development towards achieving efficient photon-harvesting medium for possible application in photonic devices. The second part of this contribution reports on the self-assembly/molecular recognition of a specific class of porphyrins giving rise to tubular nano-systems with potential THG nonlinear properties.

In this work, we investigated the nonlinear optical absorption properties of chloroaluminum, chlorogallium, chloroindium, zinc and lead octaphenoxy phthalocyanines in a dimethyl sulphoxide solution using 5 ns pulses at 532 nm. Using the Z-scan technique, the nonlinear optical properties and the excited state absorption cross-sections were determined by fitting the Z-scan data. The k value was the highest for Pb derivative at 211, making it the best nonlinear optical material. In terms of hyperpolarizability, Pb derivative (containing a larger central metal) also gave the largest value followed by aluminum derivative (containing a small central metal). The distortion of the ring caused by the central metal is used to explain the hyperpolarizability values. Large nonlinear absorption coefficient values, β_eff, in the range of 3.558–4.763 × 10^-9 cm.W^-1 and low saturation fluence values, F_sat between 21.5–38.5 mJ.cm^-2, were obtained for these samples.

Zinc phthalocyanine with S-aryl groups at α-positions have been synthesized and its optical, emission, electrochemical and third-order nonlinear optical properties were investigated. Both the Soret and Q-bands were red-shifted and obeyed Beer–Lambert's law. Electrochemical properties indicated that both oxidation and reduction processes were ring centered. Emission spectra were recorded in different solvents and the fluorescence yields obtained were in the range of 0.02 while time-resolved fluorescence data revealed lifetimes of typically few ns. Excited state dynamics in this novel thio-zinc phthalocyanine molecule has been investigated using femtosecond (fs) degenerate pump-probe spectroscopy. Nonlinear optical properties of this molecule have been examined using the Z-scan technique with picosecond (ps) and fs pulses. Both open and closed aperture Z-scan curves were recorded with ~2 ps/~150 fs laser pulses at a wavelength of 800 nm and nonlinear optical coefficients were extracted from both the studies. Degenerate pump-probe data performed at 600 nm suggested a single long lifetime of ~300 ps, possibly originating from the non-radiative decay of S₁ state.

Zinc phthalocyanine possessing triphenylamine at its peripheral position has been synthesized and its optical, emission, electrochemical and third-order nonlinear optical (NLO) properties were investigated. Soret band was broadened due to the presence of triphenylamine moiety. Electrochemical properties indicated that both oxidation and reduction processes were ring centered. Emission spectra were recorded in different solvents and the fluorescence yields obtained were in the range of 0.02–0.17 while the time-resolved fluorescence data revealed radiative lifetimes of typically few ns. Third-order NLO properties of this molecule have been examined using the Z-scan technique with picosecond (ps) and femtoseocnd (fs) pulses. Closed and open aperture Z-scan data were recorded with 2 ps/1 50 fs laser pulses at a wavelength of 800 nm and NLO coefficients were extracted from both the data. Our data clearly suggests the potential of this molecule for photonics applications.

Optical limiting properties of 2,6-dibromo-3,5-distyrylBODIPY dyes were investigated by using the z-scan technique at 532 nm in the nanosecond pulse range. A strong reverse saturable absorption response was observed even in solution, which suggests that compounds of this type are potentially suitable for use in optical limiting applications.

The synthesis and characterization of a series of 3,5-di-$p$-benzyloxystyrylBODIPY dyes with different substituents at the meso-aryl position is reported. The photophysical and nonlinear optical properties are described. BODIPYs of this type are found to be suitable for optical limiting at 532 nm on the nanosecond timescale. An enhancement of the population of the T${}_{\mathrm{\text{1}}}$ state through the incorporation of bromine atoms at the 2,6-positions does not result in an enhancement of the optical limiting properties on a nanosecond timescale. This suggests that, in contrast with phthalocyanines, access to excited state absorption (ESA) from the T${}_{\mathrm{\text{1}}}$ state through the introduction of a heavy atom effect does not provide a significantly improved reverse saturable absorbance response compared to ESA from the S${}_{\mathrm{\text{1}}}$ state.

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.

The results of recent studies on the optical limiting properties of BODIPY dyes at 532 and 1064 nm are described and compared. The optical limiting properties of novel 1,7-dimethyl-3,5-di-4-dihydroxyborylstyryl- and 3,5,7-tristyryl-1-methyl-BODIPY dyes were studied in CH₂Cl₂ and C₆H₆ and polystyrene thin films using the open aperture Z-scan technique at 532 nm with nanosecond laser pulses to provide an example of how the effective nonlinear absorption coefficient, the third order susceptibility, hyperpolarizability and limiting thresholds can be calculated.

The synthesis and characterization of a novel dibrominated 1,3,5-tristyrylBODIPY dye is reported, and its potential utility as a singlet oxygen photosensitizer and optical limiting material is assessed. The main spectral band lies in the therapeutic window, and there is a moderately high singlet oxygen quantum yield making the dye potentially suitable for use in biomedical applications and as an optical limiting dye at 532 nm. The optical limiting parameters are comparable to those reported previously for 3,5-distyrylBODIPYs, which suggests that mixtures of 3,5-distyryl and 1,3,5-tristyryl compounds that are formed in Knoevenagel condensation reactions could be used for this application. Theoretical calculations are used to assess the effect of 1,3,5-tristyryl substitution. A smaller red shift of the main spectral band is observed upon styrylation at the 1-position than is the case with the 3,5-positions due to there being smaller MO coefficients at this position, limiting the utility of this structural modification method for shifting the main BODIPY spectral band further into the therapeutic window.

The optical limiting properties of crown-ether-substituted scandium(III) phthalocyaninate complexes, bis-tetra-15-crown-5-phthalocyaninates Sc[(15C5)₄Pc]${}_2^{•0}$ (I) and Sc[(15C5)₄Pc]${}_2^{-}$ (Ia), together with monophthalocyaninate [(15C5)₄Pc]Sc(OAc) (II) were measured by using the Z-scan technique (532 nm laser and pulse rate of 10 ns). It was revealed that expansion of the $\pi$-system on moving from the monomeric Sc complex II to sandwich compound I and changing the electronic state of the sandwich compound from the anionic Ia species to the neutral radical I improves the optical limiting properties. The Im[${\chi }^{(3)}$] values obtained lie in the 10${}^{-12}$–10${}^{-10}$ esu range that is consistent with those reported previously for other organic chromophores. The crystal structure of sandwich Sc(III) complex I was elucidated by means of single-crystal X-ray diffraction analysis and was used to guide a series of theoretical calculations. It was demonstrated that the application of simplified time-dependent density functional theory (sTD-DFT) calculations can provide reasonably accurate predictions for compounds of this type when the geometries of the complexes are clearly defined.

The optical limiting properties of three meso-pentafluorophenylstyrylBODIPY dyes are investigated in the presence and absence of methyl groups at the 1,7-positions that hinder free rotation of the meso-aryl group. Pentafluorophenyl groups are introduced at the meso-position, while 4-diethylaminostyryl groups are introduced at the 3- and/or 5-positions to form dyes with strong donor-$\pi$-acceptor (D-$\pi$-A) properties to enhance the dipole moment of the molecule. Favorable optical limiting properties are obtained for all three dyes, with the highest second-order hyperpolarizability value obtained for a monostyryl dye with no methyl groups at the 1,7-position. Bromination at the 2,6-positions of a 1,7-methyl substituted dye is found to result in second-order hyperpolarizability that is an order of magnitude lower than that calculated for the analogous non-halogenated dye.

The optical limiting properties of three meso-pyridyl-distyrylBODIPY dyes with differing alkyl substitution patterns at the 2,6- and 1,7-positions on the pyrrole moieties are investigated. Styryl groups are introduced at the 3,5-positions to form dyes with strong donor-$\pi$-acceptor (D-$\pi$-A) properties. Favorable optical limiting properties are obtained for all three dyes, with the highest second-order hyperpolarizability obtained for a dye that is unsubstituted at both the 2,6- and 1,7-positions suggesting that the optical limiting properties are enhanced when the meso-aryl ring can freely rotate into the plane of the BODIPY core.

The lack of suitable optical limiters that cover the entire UV-visible-NIR region has motivated research to identify novel efficient and stable optical limiting materials. There has been a strong focus on attenuating the second harmonic of Nd:YAG pulsed lasers at 532 nm on the nanosecond timescale. The photophysicochemical processes of a series of mono- and di-(4-dimethylamino)styryl-meso-pyrenylBODIPY and mono- and di-(4-dimethylamino)buta-1,3-dienyl-meso-pyrenylBODIPY dyes were studied by UV-visible absorption and fluorescence emission spectroscopy, and by determining the fluorescence and triplet state lifetimes. Z-scan measurements were carried out at a fixed concentration of 10 $\mu$M so that the effective nonlinear coefficients, third-order susceptibilities, second-order hyperpolarizabilities and limiting fluences of the dyes can be compared and trends in the structure-property relationships for these optical limiting parameters can be identified.