Experimental and Theoretical Spectroscopic Investigation on Coumarin Based Derivatives for Non-Linear Optoelectronics Application.

The spectral properties of MBTC (4-((4-((Benzo[d]oxazol-2-ylthio)methyl)-1H-1,2,3-triazol-1-yl)methyl)-7-methoxy-2H-chromen-2-one), CBTC (4-((4(((5Chlorobenzo[d]oxazol-2-yl)thio)methyl)-1H-1,2,3-triazol-1-yl)methyl)-2H-benzo[h]chromen-2-one) and TBTC (4-((4-((Benzo[d]oxazol-2-ylthio)methyl)-1H-1,2,3-triazol-1-yl)methyl)6(tertbutyl)2Hchromen-2-one) were studied in series of solvents with different polarity at room temperature to explore their solvatochromic effect and dipole moment. Stokes shift revealed a bathochromic shift with varying solvent polarity for all molecules which implies π-πtransition. The ground state and excited state dipole moment of the molecules are calculated experimentally using salvatochromic methods like Lippert-Mataga, Bakhshiev, Kawaski-chamma-viallet, and Reichardt's microscopic solvent polarity functions and computationally by density functional theory (DFT) method. It is observed that the excited state dipole moment is higher than the ground state so synthesized molecules are more polar in the excited state than in the ground state. Using the DFT method HOMO and LUMO energy values were obtained and compared with values obtained by the cyclic voltammetry. Using the values of HOMO (highest occupied molecular orbital) and LUMO (lowest unoccupied molecular orbital) we have estimated energy gap, chemical hardness (ɳ), chemical softness (s), ionization potential (IP), electron affinity (EA), electronegativity (χ), electrophilicity (ω), and chemical potential (μ) of the molecules were estimated. The energy gap of MBTC, CBTC, and TBTC were found to be low, that is 3.861 eV, 3.822 eV, and 3.801 eV respectively, this indicates molecules are more reactive and it has the easiest π-π transition. Further electrophilic and nucleophilic sites were figured out using molecular electrostatic potential (MESP) which is useful in photochemical reactions. Hence the quantum chemical calculation and spectroscopic properties of the molecules can give a better understanding of their use in an optoelectronic device.