Triphenylamine and N-phenyl carbazole-based coumarin derivatives: Synthesis, solvatochromism, acidochromism, linear and nonlinear optical properties

Erande

Sreenath³

et al. 2019

ChemistrySelect

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NLOphoric D-π-A-π-D coumarin chalcone 5 and their BF 2 complex 6 were designed, synthesized and characterized through Mass, 13 C-NMR, and 1 H-NMR analysis. Their Photophysical properties are extensively studied in solvents of different polarity. On BF 2 complexation of coumarin chalcone shows highly red shift in absorption and emission spectra compared to uncomplexed coumarin chalcone. Positive solvatochromism observed which is well supported by linear and multilinear regression analysis. For BF 2 complexed coumarinchalcone 6 the solvent dipolarity (C SdP ) is the main factor responsible for slightly red shift in absorption spectra, and also for the highly red-shift in emission spectra. Frontier molecular orbital, molecular electrostatic potential and Generalized Mulliken-Hush analysis revealed intramolecular charge transfer in these compounds. Nonlinear optical (NLO) properties for compounds 5 and 6 were studied by solvatochromic and computational method. The linear polarizability (α), first-order hyperpolarizability (β) and second-order hyperpolarizability (γ) of compounds were studied by the time dependent density functional theory using three different functionals namely B3LYP, BHHLYP and CAMÀ B3LYP with the 6-31 G (d) basis set. BF 2 complexed compound 6, show higher values for α e + α v as well as β e + β v compared to compound 5. Third order nonlinear optical susceptibility (χ (3) ) of these compounds obtained by Zscan analysis. Third-order (χ (3) ) non-linear optical properties of BF 2 complexed coumarin-chalcone 6 were observed to be several times higher than those of the uncomplexed coumarinchalcone 5 these justify the design approach.[a] S.

Section: Resultsmentioning

confidence: 83%

Pyrene Based NLOphoric D‐π‐A‐π‐D Coumarin‐Chalcone and Their Red Emitting OBO Difluoride Complex: Synthesis, Solvatochromism, Z‐scan, and Detailed TD‐DFT Studies

Erande

Sreenath³

et al. 2019

ChemistrySelect

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“…The observed “hypsochromic shifts” in the absorption and in emission are mainly due to the interaction of the solute and specific solvents. The “hypsochromic shifts” in absorption and emission are correlated with the “dielectric constant” and “refractive index” of solvents using “Lippert‐Mataga” and “Mac‐Rae” solvent polarity functions . The dyes 4a–4d show linear relationship with “Lippert‐Mataga” and the “Mac‐Rae” solvent functions with regression coefficient close to unity Figure .…”

Section: Resultsmentioning

confidence: 96%

Experimental and theoretical investigation of linear and nonlinear optical properties of ethyl‐3‐hydroxy‐2‐napthoate azo dyes by solvatochromic, computational aspects, and Z‐scan technique

J of Physical Organic Chem

Taware

Sreenath³

et al. 2020

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To investigate the effect of substituents in azo dyes on their nonlinear optical properties, four azo dyes were synthesized using ethyl‐3‐hydroxy‐2‐naphthoate as a coupler and characterized. The polarizability (α) and hyperpolarizability (β and γ) constants were determined by using solvatochromic and computational method. A group of global hybrid and range seperated hybrid functionals having different Hartree‐Fock exchange percentage were used to evaluate the NLO properties. The functional ωB97 and ωB97XD performed better in the determination of polarizability (α) and hyperpolarizability (β and γ), respectively. The observed results for polarizability and hyperpolarizability parameters were supported by highest occupied molecular orbital‐lowest unoccupied molecular orbital (HOMO‐LUMO) energy gap, Hammett‐coefficient (σ), excited‐state coefficients (σex), and hyper‐hardness (Γ) values. Third‐order NLO properties were analyzed by using Z‐scan technique. The –OCH3 substituted dye 4d shows higher value of molecular susceptibility (χ(3)), polarizability (α), and hyperpolarizability (β and γ) parameters among the studied azo dyes. They are likely to have the potential applications in optoelectronics and photonics.

“…The exact reactive sites in molecules were observed by molecular electrostatic potential (MEP) analysis . The MEP is a three dimensional diagram which provides information about the charge distribution and related properties, such as electrophilic and nucleophilic sites in the molecules.…”

Section: Resultsmentioning

confidence: 99%

NLO Properties of 2‐Napthol Monoazo Disperse Dyes by DFT and Z‐Scan Technique – A Detailed Study

Sreenath²,

Chitrambalam³

et al. 2019

ChemistrySelect

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The non‐linear and linear optical properties of 2‐napthol based four monoazo dyes were examined by computational and Z‐scan methods. Time‐dependent (TD)‐density functional theory (DFT) computations were used to evaluate the linear polarizability (α), first‐order hyperpolarizability (β) and second‐order hyperpolarizability (γ) using global hybrid and range separated hybrid functionals at 6–311+ G (d) basis set. The functional, ωB97 performed better in the determination of linear polarizability (α) and ωB97X−D performed better in the determination of the first‐order hyperpolarizability (β) and second‐order hyperpolarizability (γ) among the global hybrid and range separated hybrid functionals. To support our theoretical findings for α, β, and γ, we have correlated with the Hammett‐coefficient (σ), excited state coefficient (σex) as well as by hyper‐hardness (Γ) relations. Third order NLO parameters – non‐linear refractive index (η2), non‐linear absorption coefficient (β), real parts and the imaginary parts of third order susceptibility (χ(3)), and second order hyperpolarizability (γ) were investigated by close and open aperture methods using Z‐scan technique. The –NO2 substituted dye 2 shows higher value of molecular susceptibility (χ(3)), polarizability (α), and hyperpolarizability (β, γ) parameters among the studied azo dyes. They are likely to have potential applications in optoelectronics and photonics.