New 1,3,4-thiadiazole compounds: synthesis, spectroscopic characterisation and theoretical analyses based on DFT calculations

Öz

In this study, four novel 1,3,4-thiadiazole compounds, derived from α-methyl cinnamic acid, were synthesised. The structural elucidation was carried out using UV-Vis, FT-IR, 1H-NMR and 13C-NMR spectroscopy. In addition, the chemical and electronic properties of the compounds as well as UV-Vis, IR and NMR analyses were theoretically performed using the density functional theory (DFT). Based on the frontier molecular orbital (FMO) energies of the compounds, which were obtained from different methods and basis sets, some chemical reactivity parameters and their relationship with the methods were analysed. Theoretical calculations were compared with the experimental results. The electronegative substituents Cl and NO2 reduced the HOMO–LUMO energy gap (ΔE), and the ones caused a bathochromic shift in the UV absorption wavelength. The Pearson correlation coefficients between the experimental and theoretical IR and 13C NMR results were approximately R = 0.99. It was seen that, the chemical shift of hydrogen bound to an electronegative nitrogen atom was affected by intarmolecular hydrogen bond interactions.

Anahtar Kelimeler

• 1 3 4-thiadiazoles
• α-methyl cinnamic acid
• computational chemistry
• density functional theory

Yeni 1,3,4-tiadiazol bileşikleri: sentez, spektroskopik karakterizasyon ve DFT hesaplamalarına dayanan teorik analizler

Öz

Bu çalışmada, α-metil sinnamik asitten türetilen dört yeni 1,3,4-tiadiazol bileşiği sentezlendi. Bileşiklerin yapısal özellikleri UV-Vis, FT-IR, 1H-NMR ve 13C-NMR spektroskopisi kullanılarak incelendi. Buna ek olarak, bileşiklerin kimyasal ve elektronik özelliklerinin yanı sıra UV-Vis, IR ve NMR analizleri teorik olarak yoğunluk fonksiyonel teorisi (DFT) kullanılarak gerçekleştirildi. Farklı yöntemler ve baz setleri kullanılarak elde edilen, bileşiklerin sınır moleküler orbital (FMO) enerjilerine dayanılarak, bazı kimyasal reaksiyon parametreleri ve bunların kullanılan yöntemlerle ilişkisi analiz edildi. Teorik hesaplamalar deney sonuçları ile karşılaştırıldı. Elektronegatif Cl ve NO2 sübstitüentlerinin HOMO-LUMO enerji aralığını (ΔE) düşürdüğü ve UV-absorbsiyon dalga boyunda bir batokromik kaymaya neden olduğu gözlendi. Deneysel ve teorik IR ve 13C NMR sonuçları arasındaki Pearson korelasyon katsayıları yaklaşık olarak R = 0.99 olarak hesaplandı. Elektronegatif azot atomuna bağlı hidrojenin kimyasal kaymasının, molekül içi hidrojen bağı etkileşimlerinden etkilendiği gözlendi.

Anahtar Kelimeler

• 1 3 4-tiadiazol
• α-metil sinnamik asit
• hesaplamalı kimya
• yoğunluk fonksiyonel teorisi

Kaynakça

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