Frontiers in Materials (Aug 2021)

Exploration of Nonlinear Optical Properties of Triphenylamine-Dicyanovinylene Coexisting Donor-π-Acceptor Architecture by the Modification of π-Conjugated Linker

  • Muhammad Usman Khan,
  • Muhammad Khalid,
  • Sumreen Asim,
  • Momina,
  • Riaz Hussain,
  • Khalid Mahmood,
  • Javed Iqbal,
  • Muhammad Nadeem Akhtar,
  • Amjad Hussain,
  • Muhammad Imran,
  • Ahmad Irfan,
  • Akbar Ali,
  • Muhammad Fayyaz ur Rehman,
  • Yang Jiang,
  • Changrui Lu

DOI
https://doi.org/10.3389/fmats.2021.719971
Journal volume & issue
Vol. 8

Abstract

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High-tech electronic, optics, and storage devices require organic compounds with nonlinear optical (NLO) properties. This study designed D-π-A based dyes with donor triphenylamine (TPA) and acceptor dicyanovinylene (DCV) species by structurally modifying π-conjugated linkers. Our density functional theory (DFT) computations analyzed the impact of structural variations on the nonlinear optical (NLO) response of newly designed dyes. The B3LYP/6-31G(d,p) level determined the quantic chemical insights: frontier molecular orbital (FMOs), natural bond orbitals (NBOs), and nonlinear optical (NLO) properties of the designed dyes (DPTM-1 to DPTM-12). UV-Vis analysis based on the TD-DFT/CAM-B3LYP/6-311+G(d,p) level explored the optoelectronic properties. DPTM-1 and DPTM-5 showed the highest red-shifted absorption band at 519 and 506 nm. NBO analysis shows that DPTM-1 to DPTM-12 dyes have positive values for all donors (D) and π-spacers but negative values for acceptors (A). The π-spacers act as a conveyer between donor and acceptor moieties; thus, electrons were transferred smoothly from D to A units, which resulted in a charge separation state. Our calculations show the extent of NLO response in terms of electronic transitions, polarizability <α>, and first hyperpolarizability (β) values. The highest value of βtotal was 110,509.23 a.u. manifested in DPTM-6 due to 2,5-dimethyloxazole as a second π-linker, twice that of R (66,275.95 a.u.). Also, DPTM-6 and DPTM-8 exhibit the lowest energy band gap of 2.06 and 2.04 eV, respectively. In short, all DPTM-1 to DPTM-12 dyes manifested maximum absorption, lowest energy band gap, greater charge transfer from donor to the acceptor, and better first hyperpolarizability values as compared to the R and showed good NLO response. The present work represents new compounds with remarkable NLO properties and their applications in modern high-tech devices.

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