2‐(1, 1‐dioxidobenzo[b]thiophen‐3(2H)‐ylidene)malononitrile (BTD) Based Styryl Chromophores‐ Solvatochomic and Computational Investigation of Linear and NLO properties. Issue 48 (21st December 2018)

• Record Type: Journal Article
• Authors: Bhagwat, Archana A.; Sekar, Nagaiyan
• Is Part Of: ChemistrySelect. Volume 3:Issue 48(2018)
• Page Start: 13654
• Page End: 13664
• Publication Date: 2018-12-21
• Subjects: Absorption -- Charge transfer -- DFT and TD-DFT -- NLO -- Solvatochromism; Chemistry -- Periodicals; 540.5
• DOI: 10.1002/slct.201803256
• Languages: English
• ISSNs: 2365-6549

Abstract

Abstract: Linear and nonlinear optical properties of the twelve styryl dyes are investigated using density functional theory (DFT). Range‐separated hybrid CAM−B3LYP and global hybrid BHandHLYP estimate high second order hyperpolarizability. Mean polarizability ( α0 ), polarizability anisotropy ( Δα ), static first‐order hyperpolarizability ( β0 ) and second hyperpolarizability ( γ ) were found to be overestimated in CAM−B3LYP than in BHandHLYP. As bond length alternation (BLA) increases first order hyperpolarizability increases. Multilinear regression analysis (MLR) shows the solvent basicity, polarizability and dipolarizabilty are responsible for absorption solvatochromism. The ratio of the dipole moments increases as donor strength and conjugation increases which support charge transfer. The figure of merit (FOM) and intrinsic hyperpolarizability found more in chromophores with dialkylamine donors. As the stability indicated by electrophilicity indices decreases the hyperpolarizability increases. Interrelationships between α0, β0 and γ were evaluated and it shows good linear fit. Absorption is red shifted and hyperpolarizability increases with the amplitude of the sine‐shaped potential along the conjugation chain. A high molecular electrostatic potential was observed in dyes containing 2‐piperidinothiophene donor. Abstract : Twelve Donor‐π‐Acceptor (D‐π‐A) styryl dyes were optimized by Density Function Theory (DFT). The effect of donor stength and conjugation length on optical and nonlinear optical properties were studied. Nonlinear optical properties derived by B3LYP/6‐311+G(d, p)CAM−B3LYP and B3LYP/6‐311+G(d, p) BHandHLYP methods. Absorption solvatochromism was studied by multilinear regression analysis.