Theoretical Studies on Electronic Spectra and Second‐order Nonlinear Optical Properties of Glucosyl Substituted Barbituric Acid Derivatives

Abstract

AM1 semi-empirical method was used to optimize the barbituric acid derivatives substituted with glucosyl B 1-5 (series B), and the thiobarbituric acid derivatives substituted with glucosyl T 1-5 (series T). Based on the optimized structures, INDO/CI method was adopted to calculate the electronic spectra. Meanwhile, the second-order nonlinear optical (NLO) coefficients β µ were calculated with the sum-over-state (SOS) formula. The results show that when the number of glucosyl units was increased, |β µ | values of the barbituric and thiobarbituric acid derivatives were both enhanced, especially for thiobarbituric acid derivatives. It indicates that non-conjugated substituted group could also improve NLO properties of materials when the number of repeated units was increased. Additionally, the absorption bands appearing in UV area are consistent with the proper change of the number of glucosyl units, and consequently it can be concluded that the high transparencies of all systems were scarcely varied.

Structural parameter-modulated nonlinear optical amplitude of acceptor–π–D–π–donor-configured pyrene derivatives: a DFT approach

“…4 The p-based electronic delocalization permits organic compounds to exhibit rapid response times, resulting in promising NLO responses. 5,6 The non-centrosymmetric pconjugated spacer compounds boost the charge transfer process among electron-donors (D) and acceptors (A), accomplishing 1 st , 2 nd and 3 rd order nonlinear amplitudes. The NLO materials have demonstrated large intramolecular charge transference (ICT), transmission of donor-acceptor p-clouds via p-linkers, higher ground electronic state dipole moments, along with excited transition states.…”

Possible Application of the Organic Barbiturates as NLO Materials

“…Yield 91%. The interaction of 5-hydroxy-L-tryptophan with the violuric acid leads to isolation of the yellow crystals of the neutral 5-hydroxy-L-tryptophan dihydrate (9), whose structure is also reported for the first time (see Figure S5).…”

“…Moreover, there are already known barbituric acid derivatives which exhibit NLO properties. , There is also the possibility of designing polar cocrystals made up of barbituric acid and urea molecules of different polymorphic modifications, crystallizing in noncentrosymmetric space groups . Second-order nonlinear optical properties have been reported for tetrathiafulvalene-π-(thio)barbituric acid chromophores, glucosyl-substituted barbiturates, and aniline derivatives of barbituric acid. − In the case of organic crystals containing VA anions, however, the limits to the wide application of these derivatives as NLO materials are evident; deprotonation of the OH group of violuric acid leads to formation of the CNO- species, and the corresponding n → π* transition is responsible for the absorption band observed within the 500−665 nm region . To avoid these difficulties observed for VA derivatives, the search for new VA-based organic materials must be focused on a study of the interaction of VA with heterocyclics possessing weaker basic properties, which could crystallize containing neutral VA.…”

Structure, charge density, and Hirshfeld surface analysis of proton transfer complex 2‐amino‐4‐methylpyridinium 2‐(3‐methylphenyl)‐acetate

“…Such studies aid in understanding the features of chemical bonding in molecules from the topological analysis of electron densities [ 3 ] and various electrostatic properties of molecules. Over the past three decades, charge density distribution of several materials like magnetic, [ 4,5 ] energetic, [ 6 ] NLO, [ 7–11 ] and molecular complexes with biological properties have been reported. [ 12,13 ] The effect of metal atoms in ligands has been analyzed using the topological properties of electron density.…”