Unsymmetrical β-functionalized ‘push–pull’ porphyrins: synthesis and photophysical, electrochemical and nonlinear optical properties

Abstract

A new family of unsymmetrical β-TPA appended ‘push–pull’ porphyrins has been synthesized in good yield for the first time. They exhibited red shifted broad absorption spectral features with high dipole moments and tunable redox properties.

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

“…Our group has recently reported the NLO properties of two unsymmetrically substituted novel porphycenes, i.e., 2,7,12,13-tetraethyl-9,10,19,20-tetramethyl(OAPo-T) and 2,3,16,17-tetraethyl-9,10,19,20-tetramethyl (OAPo-C) porphycenes with TPA cross-sections of 159 and 145 GM, respectively, obtained with exact experimental conditions (kHz, fs pulses at 800 nm) used in the present study. Similarly, one of our earlier works ( Rathi et al, 2020 ) reported fs, MHz NLO data of novel porphyrins [H 2 TPP(TPA) 2 NO 2 , H 2 TPP(TPA) 2 CHO, ZnTPP(TPA) 2 NO 2 , and ZnTPP(TPA) 2 CHO]. The obtained β values were ∼10 −8 cm/W, σ TPA values of ∼10 5 GM, n 2 values of ∼10 −13 cm 2 /W, and χ (3) values of ∼10 −11 e.s.u.…”

“…Our group has recently reported the NLO properties of two unsymmetrically substituted novel porphycenes, i.e., 2,7,12,10,19, and 2, 3,16,10,19, porphycenes with TPA crosssections of 159 and 145 GM, respectively, obtained with exact experimental conditions (kHz, fs pulses at 800 nm) used in the present study. Similarly, one of our earlier works (Rathi et al, 2020) (3) values of ∼10 −11 e.s.u. for those molecules.…”

“…Promising novel organic molecules, possessing significant nonlinear optical (NLO) characteristics, are in high demand for various device applications in the fields of photonics, biomedical imaging, optical communications, etc., ( Anusha et al, 2015 ; Venkatram et al, 2008a ). All these organic molecules, like phthalocyanines ( Rao et al, 2000 ; Maya et al, 2003 ; Swain et al, 2014b ; Bharati et al, 2018 ; Venkatram et al, 2008b ), porphyrins, and corroles ( Anusha et al, 2012 ; Sarma et al, 2011 ) are reported frequently possessing strong third-order NLO coefficients and cross-sections ( Swain et al, 2014a ; Bhattacharya et al, 2019a ; Clavian et al, 2019 ; Katturi et al, 2020a ; Katturi et al, 2020b ; Pati et al, 2020 ; Rathi et al, 2020 ; Kumar et al, 2021 ). Phthalocyanines generally have strong colors and are used as dyes.…”

“…To revive the study of the potential of NLO in the field of telecommunication, photonics, biomedicine, and optical signal processing, several NLO moieties were designed through various π-conjugated organic molecules ( Mardar, 2006 ; Bures et al, 2012 ; Sofiani et al, 2016 ; Biswas et al, 2020 ). For this reason, a great variety of small organic molecules and macrocyclic systems, such as porphyrins ( Rao et al, 2000 ; Senge et al, 2007 ; Swain et al, 2014a ; Katturi et al, 2020b ; Rathi et al, 2020 ; Vijisha et al, 2020 ; Kumar et al, 2021a ), phthalocyanines ( de la Torre et al, 2004 ; Kumar et al, 2007 ; Swain et al, 2014b ; Zhang et al, 2014 ; Bharati et al, 2018 ; Venkatram et al, 2018a; Venkatram et al, 2018b; Bhattacharya et al, 2019a ; Bhattacharya et al, 2019b ; Bhattacharya et al, 2021 ), corroles ( Katturi et al, 2020a ; Lu et al, 2021 ), porphycenes ( Sarma et al, 2011 ; Swain et al, 2012 ; Pati et al, 2020 ), and BODIPY dyes ( Ngoy et al, 2019 ), have been investigated for their NLO properties. Of these systems, we are particularly interested in phthalocyanine-based macrocyclic systems toward these applications.…”

Direct Cobalt‐Catalyzed Phosphorylation of Porphyrins

“…The possibility of various types of chemical modification of these macrocycles at the periphery and in the coordination center resulting in the formation of strong metal complexes allows us to classify them as excellent preparations for photodynamic cancer therapy, electro-and photocatalysts for reduction and oxidation, light energy converters, materials with nonlinear optical properties, organic semiconductors and liquid crystals. [1][2][3][4][5][6][7][8][9][10] Porphyrin derivatives, acting as dyes and catalysts, play a vitally important role in a variety of processes, such as photosynthesis, breathing, and cell metabolism. [11][12][13][14][15] A lot of methods have been developed for porphyrin modification to change their physico-chemical properties.…”