Polycyclic aromatic hydrocarbon-substituted push-pull chromophores: an investigation of optoelectronic and nonlinear optical properties using experimental and theoretical approaches

DENGİZ Ç.

TURKISH JOURNAL OF CHEMISTRY, cilt.45, sa.5, ss.1375-1424, 2021 (SCI-Expanded) identifier identifier identifier identifier

  • Yayın Türü: Makale / Tam Makale
  • Cilt numarası: 45 Sayı: 5
  • Basım Tarihi: 2021
  • Doi Numarası: 10.3906/kim-2102-22
  • Dergi Adı: TURKISH JOURNAL OF CHEMISTRY
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus, Academic Search Premier, Chemical Abstracts Core, TR DİZİN (ULAKBİM)
  • Sayfa Sayıları: ss.1375-1424
  • Anahtar Kelimeler: polycyclic aromatic hydrocarbon, chromophore, charge-transfer, push-pull, [2+2] ccycloaddition-retroelectrocyclization, CHARGE-TRANSFER CHROMOPHORES, 2+2 CYCLOADDITION, 7,7,8,8-TETRACYANOQUINODIMETHANE TCNQ, REDOX BEHAVIOR, DONOR, MOLECULES, TETRACYANOETHYLENE, PERFORMANCE, ACCEPTORS, CHEMISTRY
  • Orta Doğu Teknik Üniversitesi Adresli: Evet

Özet

A series of new push-pull chromophores were synthesized in moderate to very high yields (65%-97%) by treating TCNE and TCNQ with alkynes substituted by electron-rich diethylaniline and polycyclic aromatic hydrocarbons. Some of the chromophores exhibit strong intramolecular charge-transfer bands in the near-1R region with lambda(max). values between 695 and 749 nm. With the help of experimental and theoretical analysis, it is concluded that the trend in lambda(max) values is affected by PAH substituents sterically, not electronically. Steric constraints led to the increased dihedral angles, reducing conjugation efficiencies. The absorption properties of push-pull compounds have been investigated in solvents possessing different polarities. All chromophores exhibited positive solvatochromism. As an additional proof of efficient charge-transfer in push-pull chromophores, quinoid character (dr) values were predicted using calculated bond lengths. Remarkably, substantial dr values (0.045-0.049) were predicted for donor diethylaniline rings in all compounds. The effects of various polycyclic aromatic hydrocarbons on optical and nonlinear optical properties were also studied by computational methods. Several parameters, such as band gaps, Mulliken electronegativity, chemical hardness and softness, dipole moments, average polarizability, first hyperpolarizability, were predicted for chromophores at the B3LYP/6-31+ +G(d,p) level of theory. The predicted first hyperpolarizability beta((tot)) values vary between 198 to 538 x 10(-30) esu for the reported push-pull chromophores in this study. The highest predicted beta((tot)) value in this study is 537.842 x 10(-30) esu, 8150 times larger than the predicted beta((tot)) value of benchmark NLO material urea, suggests possible utilization of these chromophores in NLO devices. The charge-transfer character of the synthesized structures was further confirmed by HOMO-LUMO depictions and electrostatic potential maps.