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

Dengiz, Cagatay

doi:10.3906/kim-2102-22

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

Çağatay DENGİZ (Orta Doğu Teknik Üniversitesi, Mühendislik Fakültesi, Kimya Bölümü, Ankara, Türkiye)

Turkish Journal of Chemistry

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Yıl: 2021 Cilt: 45 Sayı: 5 Sayfa Aralığı: 1375 - 1390 Metin Dili: İngilizce DOI: 10.3906/kim-2102-22 İndeks Tarihi: 30-06-2022

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

Öz:

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-IR region with $λ_max$ values between 695 and 749 nm. With the help of experimental and theoretical analysis, it is concluded that the trend in $λ_max$ 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 $β_(tot)$ values vary between $198 to 538 × 10^{–30}$ esu for the reported push–pull chromophores in this study. The highest predicted $β_(tot)$ value in this study is $537.842 × ^{10–{30$ esu, 8150 times larger than the predicted $β_(tot)$ 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.

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APA	Dengiz C (2021). Polycyclic aromatic hydrocarbon-substituted push–pull chromophores: an investigation of optoelectronic and nonlinear optical properties using experimental and theoretical approaches. , 1375 - 1390. 10.3906/kim-2102-22
Chicago	Dengiz Cagatay Polycyclic aromatic hydrocarbon-substituted push–pull chromophores: an investigation of optoelectronic and nonlinear optical properties using experimental and theoretical approaches. (2021): 1375 - 1390. 10.3906/kim-2102-22
MLA	Dengiz Cagatay Polycyclic aromatic hydrocarbon-substituted push–pull chromophores: an investigation of optoelectronic and nonlinear optical properties using experimental and theoretical approaches. , 2021, ss.1375 - 1390. 10.3906/kim-2102-22
AMA	Dengiz C Polycyclic aromatic hydrocarbon-substituted push–pull chromophores: an investigation of optoelectronic and nonlinear optical properties using experimental and theoretical approaches. . 2021; 1375 - 1390. 10.3906/kim-2102-22
Vancouver	Dengiz C Polycyclic aromatic hydrocarbon-substituted push–pull chromophores: an investigation of optoelectronic and nonlinear optical properties using experimental and theoretical approaches. . 2021; 1375 - 1390. 10.3906/kim-2102-22
IEEE	Dengiz C "Polycyclic aromatic hydrocarbon-substituted push–pull chromophores: an investigation of optoelectronic and nonlinear optical properties using experimental and theoretical approaches." , ss.1375 - 1390, 2021. 10.3906/kim-2102-22
ISNAD	Dengiz, Cagatay. "Polycyclic aromatic hydrocarbon-substituted push–pull chromophores: an investigation of optoelectronic and nonlinear optical properties using experimental and theoretical approaches". (2021), 1375-1390. https://doi.org/10.3906/kim-2102-22

APA	Dengiz C (2021). Polycyclic aromatic hydrocarbon-substituted push–pull chromophores: an investigation of optoelectronic and nonlinear optical properties using experimental and theoretical approaches. Turkish Journal of Chemistry, 45(5), 1375 - 1390. 10.3906/kim-2102-22
Chicago	Dengiz Cagatay Polycyclic aromatic hydrocarbon-substituted push–pull chromophores: an investigation of optoelectronic and nonlinear optical properties using experimental and theoretical approaches. Turkish Journal of Chemistry 45, no.5 (2021): 1375 - 1390. 10.3906/kim-2102-22
MLA	Dengiz Cagatay Polycyclic aromatic hydrocarbon-substituted push–pull chromophores: an investigation of optoelectronic and nonlinear optical properties using experimental and theoretical approaches. Turkish Journal of Chemistry, vol.45, no.5, 2021, ss.1375 - 1390. 10.3906/kim-2102-22
AMA	Dengiz C Polycyclic aromatic hydrocarbon-substituted push–pull chromophores: an investigation of optoelectronic and nonlinear optical properties using experimental and theoretical approaches. Turkish Journal of Chemistry. 2021; 45(5): 1375 - 1390. 10.3906/kim-2102-22
Vancouver	Dengiz C Polycyclic aromatic hydrocarbon-substituted push–pull chromophores: an investigation of optoelectronic and nonlinear optical properties using experimental and theoretical approaches. Turkish Journal of Chemistry. 2021; 45(5): 1375 - 1390. 10.3906/kim-2102-22
IEEE	Dengiz C "Polycyclic aromatic hydrocarbon-substituted push–pull chromophores: an investigation of optoelectronic and nonlinear optical properties using experimental and theoretical approaches." Turkish Journal of Chemistry, 45, ss.1375 - 1390, 2021. 10.3906/kim-2102-22
ISNAD	Dengiz, Cagatay. "Polycyclic aromatic hydrocarbon-substituted push–pull chromophores: an investigation of optoelectronic and nonlinear optical properties using experimental and theoretical approaches". Turkish Journal of Chemistry 45/5 (2021), 1375-1390. https://doi.org/10.3906/kim-2102-22