Yapısal, Spektroskopik ve Elektronik Özellikler Üzerine Ab-initio Çalışması (E)-1-(4-Methoxyanthracen-1-yl)-2-phenyldiazen Azo boyaları Molekül

Öz

(E)-1-(4-Methoxyanthracen-1-yl)-2-phenoldiazene veya C_21 H_16 N_2 O, günümüzde birçok endüstride bir algılayıcı molekül olarak en çok kullanılan bileşik olan tautomer azo boyalarından biridir. Bildiğimiz gibi, mevcut ticari azo boyaların %90'dan fazlası totomerik boyalardır (Kelemen, 1981). Kuantum kimyası hesaplamaları, gelecekteki uygulamalar için moleküler bileşiklerin yapıları ve elektrokimyasal özellikleri arasındaki ilişkiyi netleştirebilir. Deneysel ve teorik hesaplamaların karşılaştırılması, doğru atamaların yapılmasında ve moleküler yapılar ile özellikleri arasındaki ilişkinin anlaşılmasında çok faydalı olabilir. Bu çalışmada temel amaç, başlık molekülünün ((E)-1-(4-Methoxyanthracen-1-yl)-2-phenyldiazene) yapısal geometrilerinin, ab-initio yöntemi kullanılarak spektroskopik ve elektronik özelliklerinin karakterize edilmesidir. yoğunluk fonksiyonel teorisi (DFT) üzerine (Becke, 1988; Becke, 1993). Temel durumdaki başlık molekülünün moleküler geometrisi ve titreşim spektroskopisi, 6-311G (d,p) temel seti ile DFT/B3LYP yöntemi uygulanarak hesaplanmıştır. Bağ uzunluğu, bağ açısı ve dihedral açı gibi yapısal özellikler, mevcut deney verileriyle mükemmel bir uyum içindedir (Crochet ve diğerleri, 2011). Başlık molekülünün 114 titreşim modu, germe, düzlem içi bükülme, düzlem dışı bükülme ve burulma titreşimleri ile belirtilmiştir. Dimetil sülfoksit (DMSO) çözücü içindeki UV absorpsiyon spektrumları, zamana bağlı yoğunluk fonksiyonel teorisi (TD-DFT) kullanılarak tahmin edilmiştir (Ronca ve diğerleri, 2014). Ayrıca, DFT/B3LYP yöntemi dahilinde Gauge-Invariant Atomic Orbital (GIAO) yaklaşımı kullanılarak DMSO solventinde 1H ve 13C NMR kimyasal kaymaları hesaplanmıştır (Scott ve Radon, 1996; Wolinskiet ve diğerleri, 1997). Son olarak, başlık molekülünün elektronik özellikleri, En Düşük Boş Moleküler Orbital - En Yüksek Dolu Moleküler Orbital (HOMO-LUMO) etkileşimini belirlemeyi sağlayan Koopman teoremi kullanılarak da elde edilmiştir (Sastri ve Perumareddi, 1997; Pearson, 1986). Bu molekülün, termodinamik olarak kararlı ve dayanıklı, düşük iyonizasyon potansiyel enerjisine (IP) işaret eden 1.5 eV'den büyük boşluk enerjisine (Örn) sahip olduğu, elektronunu kolayca kaybettiği için indirgeyici ajan olma eğiliminde olduğu, yaklaşık 2.43 eV elektron afinitesi olduğu bildirilebilir. (EA), iyi iletken özelliklere, başlık molekülünün polar bir karakter olduğunu gösteren yüksek elektronegatifliğe (x), düşük kimyasal sertlik değerine (ƞ) ve global elektrofiliklik indeksine sahip olduğunu belirtir.

Anahtar Kelimeler

• DFT
• UV spektrum
• kimyasal kaymalar
• elektronik özelliklek
• azo boyalar

Ab-initio Study on Structural, Spectroscopic, and Electronic Properties of (E)-1-(4-Methoxyanthracen-1-yl)-2-phenyldiazene Azo dyes Molecule

Abstract

(E)-1-(4-Methoxyanthracen-1-yl)-2-phenyldiazene or C_21 H_16 N_2 O is one of the tautomer azo dyes which is the most usable compound in several industries as a sensing molecule, nowadays. As we know, more than 90% of the existing commercial azo dyes are tautomeric ones (Kelemen, 1981). Quantum chemistry calculations can clarify the relationship between structures and electrochemical properties of molecular compounds for future applications. A comparison of the experimental and theoretical calculations can be very useful in making correct assignments and understanding the relationship between molecular structures and their properties. In this study, the main purpose is to characterize the structural geometries of the title molecule ((E)-1-(4-Methoxyanthracen-1-yl)-2-phenyldiazene), spectroscopic and electronic properties by utilizing ab-initio method based on density functional theory (DFT) (Becke, 1988; Becke, 1993). The molecular geometry and vibrational spectroscopy of the title molecule, in the ground state, have been computed by applying DFT/B3LYP method with the basis set of 6-311G (d,p). The structural properties, such as bond length, bond angle, and dihedral angle, are in excellent agreement with those of available experiment data (Crochet et al., 2011). 114 vibrational modes of the title molecule have been specified with stretching, in-plane-bending, out-of-plane-bending, and torsion vibrations. UV absorption spectra within dimethyl sulfoxide (DMSO) solvent have been predicted by using the time-dependent density functional theory (TD-DFT) (Ronca et al., 2014). Moreover, 1H and 13C NMR chemical shifts have been computed in DMSO solvent by using the Gauge-Invariant Atomic Orbital (GIAO) approach within DFT/B3LYP method (Scott and Radon, 1996; Wolinskiet et al., 1997). Finally, the electronic properties of the title molecule have been also attained by using Koopman’s theorem enable to determine the Lowest Unoccupied Molecular Orbital - Highest Occupied Molecular Orbital (HOMO-LUMO) interaction (Sastri and Perumareddi, 1997; Pearson, 1986). It can be reported that this molecule has gap energy (Eg) bigger than 1.5 eV which indicates thermodynamically stable and durable, low ionization potential energy (IP) which tends to be reducing agents because it is easily losing its electron, about 2.43 eV electron affinity (EA) which denotes that it has good conductive properties, high electronegativity (x) which shows that the title molecule is a polar character, low value of chemical hardness (ƞ) and global electrophilicity index.

Keywords

• DFT
• UV absorption
• chemical shifts
• electronic properties
• azo dyes

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