Optical, Electrochemical, Third-Order Nonlinear Optical Investigations of 3,4,5-Trimethoxy Phenyl Substituted Non-Aqueous Phthalocyanines

Abstract

A new series of non-aqueous phthalocyanines having 3,4,5-trimethoxy phenyl group at peripheral positions in which the central cavity possessing Cu(II), Zn(II), and without metals has been synthesized, and its absorption, fluorescence (steady-state and excited state lifetimes), electrochemical, and third-order nonlinear optical (NLO) properties were evaluated. Absorption studies data suggest that all three phthalocyanines obey Beer–Lambert’s law, and the redox properties indicate that both oxidation and reduction reactions are macrocyclic centered. The singlet quantum yields were measured in different solvents and were found to be in the range of 0.2–0.5 in the case of free-base, whereas it was in the range of 0.1–0.5 in zinc derivative, while the time-resolved fluorescence data revealed lifetimes of typically a few ns. The third-order NLO properties were investigated using the Z-scan technique with kilohertz (for retrieving true electronic nonlinearities) and megahertz repetition rate femtosecond pulses at 800 nm. Intensity-dependent Z-scan studies revealed robust NLO coefficients for solutions and thin films (two-photon absorption cross-sections of 9,300–57,000 GM) of these molecules suggesting a strong potential for optical switching, imaging, and optical limiting applications.

Ethyl acetoacetate and acetylacetone appended hexabromo porphyrins: synthesis, spectral, electrochemical, and femtosecond third-order nonlinear optical studies

“…Banerjee et al 5 observed significantly enhanced nonlinear absorption under the occurrence of a prominent three-photon absorption (3PA coefficient of ∼10 −23 cm 3 W −2 ) in TiO 2 nanocolloids with the same experimental setup used in this work. Srivishnu et al 7 carried out their investigation of non-aqueous phthalocyanines and retrieved corresponding strong two-photon absorption cross-sections of 9300–57 000 GM. Similarly, Allu et al 6 extensively investigated the NLO responses of silver (Ag) nanowires under the excitation of a high repetition rate fs laser beam.…”

“…Hence, numerous materials are being explored for NLO properties every day. We have also conducted NLO studies on materials such as organic, inorganic compounds such as nanoentities, 5,6 phthalocyanines, 7 porphyrins, [8][9][10] etc. Porphyrins with availability of extensive optical and spectroscopy data (theoretical and experimental) have become suitable candidates for exploring their NLO responses.…”

Stability enhancement and pronounced three-photon absorption in SrCl2-doped FAPbBr3nano crystals

“…The NLO properties of Cs 2 AgBiBr 6 double PNCs, exhibiting a TPA cross-section of B1906 GM and TPA coefficient of B10 À11 cm W À1 , were investigated. 40 Our group has carried out extensive broadband ultrafast laser-interaction-triggered spectroscopic studies employing novel systems, such as nano entities, [41][42][43] PNCs, 29,30 and organic-inorganic compounds, [44][45][46] unveiling their exotic photonic responses in the NLO domain. In the present work, FAPbBr 3 is chosen as a prototype to investigate its interactions with Sr 2+ and Cl À ions and its advances for NLO studies.…”

Deviation from Beer's law and relationship of aggregation with the effective TPA coefficient: UV-vis studies on a series of low symmetry monophthalocyanines bearing a cyclotriphosphazene substituent

“…The ability of such molecules to form ordered ensembles (aggregates) plays a key role in the development of various optical materials. In particular, phthalocyanines exhibit excellent non-linear optical (NLO) properties, [1][2][3] which are important for application in optical technologies, primarily, in the creation of optical limiters, light filters, and signal processing devices. 4,5 Aggregation of phthalocyanines occurs due to the van der Waals interactions between macrocycles, resulting in the formation of columnar stacks.…”