Synthesis of a New Nitrile-Based Diamine, NMR Spectra and DFT Studies

Öz

Herein, 4-(Bis(4-aminophenyl)amino)-2-chlorobenzonitrile was synthesized in detail by experimental and theoretical methods. Structural confirmation of the compound was carried out by ¹H-NMR and ¹³C-NMR spectroscopy. In order to determine the electronic and optoelectronic properties of the molecule, Density Functional Theory (DFT) and Time Dependent DFT (TD-DFT) calculations were performed at the B3LYP, B3PW91 and CAM-B3LYP/6-31G levels. In the obtained UV-Vis spectrum, two characteristic absorption bands were observed, corresponding to the π→π* transition around 300 nm and the intramolecular charge transfer (ICT) transition specific to the donor-acceptor structure in the range of 480-500 nm. The ECD spectrum showed that these transitions gave optical responses with opposite signs, indicating a weak chiral asymmetry or charge distribution orientation in the molecule. The MEP map confirmed that the nitrile group is an electron acceptor and the amine groups are electron donors, and showed that the molecule exhibits a typical push-pull architecture. The calculated dipole moment values indicated that the molecule has high polarizability, while the polarizability (α ≈ 297–303 a.u.) and hyperpolarizability (β ≈ 1.55×10-34–1.90×10-34esu) values supported the second-order nonlinear optical (NLO) response potential.

Anahtar Kelimeler

• Nitrile-based diamine
• DFT
• Optoelectronic
• Nonlinear optical
• Chlorobenzonitrile
• NMR

Yeni Nitril Bazlı Diaminin Sentezi, NMR Spektrumları ve DFT Çalışmaları

Öz

Burada, 4-(Bis(4-aminofenil)amino)-2-klorobenzonitril deneysel ve teorik yöntemlerle detaylı olarak sentezlenmiştir. Bileşiğin yapısal doğrulaması 1H-NMR ve 13C-NMR spektroskopisi ile gerçekleştirilmiştir. Molekülün elektronik ve optoelektronik özelliklerini belirlemek amacıyla B3LYP, B3PW91 ve CAM-B3LYP/6-31G seviyelerinde Yoğunluk Fonksiyonel Teorisi (DFT) ve Zaman Bağımlı DFT (TD-DFT) hesaplamaları yapılmıştır. Elde edilen UV-Vis spektrumunda, 300 nm civarında π→π* geçişine ve 480-500 nm aralığında donör-akseptör yapıya özgü molekül içi yük transferi (ICT) geçişine karşılık gelen iki karakteristik absorpsiyon bandı gözlenmiştir. ECD spektrumu, bu geçişlerin zıt işaretli optik tepkiler verdiğini ve molekülde zayıf bir kiral asimetri veya yük dağılımı yönelimi olduğunu gösterdi. MEP haritası, nitril grubunun bir elektron alıcısı, amin gruplarının ise elektron vericisi olduğunu doğruladı ve molekülün tipik bir itme-çekme mimarisi sergilediğini gösterdi. Hesaplanan dipol moment değerleri, molekülün yüksek polarize edilebilirliğe sahip olduğunu gösterirken, polarize edilebilirlik (α ≈ 297–303 a.u.) ve hiperpolarize edilebilirlik (β ≈ 1,55×10-34–1,90×10-34esu) değerleri ikinci dereceden doğrusal olmayan optik (NLO) tepki potansiyelini destekledi.

Anahtar Kelimeler

• Nitril bazlı diamin
• DFT
• Optoelektronik
• Doğrusal olmayan optik
• Klorobenzonitril
• NMR

Kaynakça

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