Synthesis and Optical Characterization of Hydrazone-Substituted Push-Pull-Type NLOphores
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Tarih
2024
Dergi Başlığı
Dergi ISSN
Cilt Başlığı
Yayıncı
Amer Chemical Soc
Erişim Hakkı
info:eu-repo/semantics/openAccess
Özet
Two distinct families of NLOphores featuring hydrazone donors were synthesized using click-type [2 + 2] cycloaddition retroelectrocyclizations (CA-RE). Despite the limitations in the substrate scope, it was shown for the first time that hydrazone-activated alkynes could undergo reactions with TCNE/TCNQ. The electrochemical, photophysical, and second-order nonlinear optical (NLO) characteristics of the chromophores were analyzed utilizing experimental and computational approaches. Chromophores 17-21 and 23-27 exhibited two reduction waves, along with one oxidation wave that can be attributed to the hydrazone moiety. All chromophores exhibit charge-transfer bands extending from the visible to the near-infrared region. The lambda(max) of hydrazone-based chromophores falls within the range of 473 to 725 nm. Additionally, all chromophores exhibited positive solvatochromism. Computational studies have been performed to elucidate the origin of the low-energy absorption bands. Parameters such as dipole moment, band gaps, electronegativity, global chemical hardness/softness, average polarizability, and first hyperpolarizability were calculated to obtain information about NLO properties of the target structures. The thermal stabilities of the NLOphores were assessed through TGA. Experimental NLO measurements were conducted using the electric field-induced second harmonic generation (EFISHG) technique. The studied structures demonstrated NLO responses, with mu beta values between 520 x 10(-48) esu and 5300 x 10(-48) esu.
Açıklama
Anahtar Kelimeler
Intramolecular Charge-Transfer, 2+2 Cycloaddition-Retroelectrocyclization, Density-Functional Theory, Electron-Rich Alkynes, Highly Efficient, Solar-Cells, Chromophores, Acceptor, Molecules, Tcnq
Kaynak
Journal of Organic Chemistry
WoS Q Değeri
Q1
Scopus Q Değeri
Q2
Cilt
89
Sayı
18
