On the viability of divergent donor moieties in malononitrile-based donor-π-acceptor NLO active materials: A DFT/TD-DFT study

Yahya M., Kurtay G., Suvitha A. R.

Journal of Physical Organic Chemistry, vol.35, no.10, 2022 (SCI-Expanded) identifier identifier

  • Publication Type: Article / Article
  • Volume: 35 Issue: 10
  • Publication Date: 2022
  • Doi Number: 10.1002/poc.4403
  • Journal Name: Journal of Physical Organic Chemistry
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus, Academic Search Premier, Applied Science & Technology Source, Chemical Abstracts Core, Compendex, INSPEC
  • Keywords: ATMM, DFT, donor-pi-acceptor, malononitrile, NLO, TD-DFT
  • Hacettepe University Affiliated: No


© 2022 John Wiley & Sons Ltd.In this study, a detailed density functional theory (DFT) and time-dependent (TD)-DFT investigation of (E)-2-((5-(2-aryl)thiophen-2-yl)methylene)malononitrile backbone decorated with divergent donor subunits including triphenylamine (Q1), 2,3,6,7-tetrahydro-1H,5H-pyrido[3,2,1-ij]quinoline (Q2), 1-phenylpiperidine (Q3), 1-phenylpyrrolidine (Q4), and 4-phenylmorpholine (Q5) were conducted consecutively. During the modelization of the dye molecules, the linker and acceptor subunits were kept identical to focus on the donor scaffolds' influence on the electronic and photophysical properties. The target photosensitizers were then abbreviated according to their different donor subunits, C(1-5). Conducted computational studies reveal that these compounds have enhanced electronic properties and that their reduced bandgap (Ɛgap) energies prove their potent applicability as non-linear optical (NLO) active components. Accordingly, the dye molecules were also investigated using UV–vis absorption spectra in the presence of various solvent systems. The global chemical reactivity descriptors, molecular electrostatic potential, and first-order NLO response of C(1-5) molecules were examined, and the thermodynamic parameters of target molecules, including heat capacity, entropy, enthalpy, free energy, and zero-point energy, were also determined as a function of temperature (298.15 K).