2-Metoksipiridin-3-Boronik Asitin Lineer Olmayan Özellikleri, Konformasyonel, Titreşimsel ve Elektronik Yapısı Üzerine Substitüent Etkisinin Kuantum Mekanik Metodlar ile Araştırılması

Year 2019, Volume: 12 Issue: 1, 14 - 24, 24.03.2019

Güventürk Uğurlu

https://doi.org/10.18185/erzifbed.416682

Cited By: 1

Abstract

Bu çalışmada, 2-metoksipiridin-3-boronik asit (I) ve 6-sübstitüe-2-metoksipiridin-3-boronik asit türevleri; 6-floro-2-metoksipiridin-3-boronik (II) ve 6-kloro-2-metoksipiridin-3- boronik asit (III) moleküllerinin yapısal parametreleri, titreşim frekansları, dipol moment (μ), polarizebilite (α) ve hiperpolarizebilite (β) değerleri Hartree Fock (HF) ve Yoğunluk Fonksiyonel Teorisi (DFT/B3LYP) metotlarında 6-311 ++ G (d, p) temel seti kullanılarak hesaplatıldı. I, IIve III moleküllerinin en yüksek dolu molekül orbital (HOMO) ve en düşük boş molekül orbital (LUMO) aynı metot-temel seti kombinasyonu ile hesaplandı ve enerji aralıkları (ΔEg) incelendi.   ¹H ve ¹³C-NMR kimyasal kayma değerleri GIAO yaklaşımına göre gaz fazında B3LYP/6-311+G (2d,p) ve HF/6-31G (d) yöntemleri ile hesalandı. Ayrıca, moleküllerin potansiyel enerji yüzeyi (PEY), C1-C2-B-O1 dihedral açısının fonksiyonu olarak her iki metotta 6-31+G temel seti kullanılarak yapıldı. Hesaplanan PEY üzerinde 0˚, 140˚, 220˚ ve 360˚’ de minimum, 90˚, 180˚ ve 270˚ de ise maksimumlar yer almaktadır. Moleküllerin hiperpolarizebilite değerlerinin sıralaması III>II>Işeklindedir. En büyük bariyer yüksekliğine180˚ de I molekülünün sahip olduğu görüldü.  I, IIve IIImoleküllerinin dipol moment değerleri sırasıyla, B3LYP / 6-311 ++ G (d, p) metot-temel seti kombinasyonu ile 1.18, 1.19 ve1.25 HF / 6-311 ++ G (d, p) metot-temel seti kombinasyonu 1.17, 1.16 ve 1.30 Debye bulundu. Her iki metotta hesaplanan I molekülünün yapısal parametreleri, literatürdeki verilerle karşılaştırıldı ve yapısal parametreler arasında iyi bir uyum olduğu görüldü.

Keywords

2-metoksipiridin-3-boronik asit, Polarizebilite, HF, DFT / B3LYP, ∆E

Investigation of Substitute Effect on Non-Linear Properties, Conformational, Vibrational and Electronic Structure of 2-Methoxypyridine-3-Boronic Acid by Quantum Mechanical Methods

Abstract

In this study, the values of structural parameters, vibration frequencies, dipole moment (μ), polarizability (α), hyperpolarizability β) of 2-methoxypyridine-3-boronic acid (I) and 6-substituted-2-methoxypyridine-3-boronic acid derivatives; 6-fluoro-2-methoxypyridine-3-boronic (II) and 6-chloro-2-methoxypyridine-3-boronic acid (III) molecules have been calculated at Hartree Fock (HF) and Density Functional Theory (DFT / B3LYP) with 6-311++G (d, p) basis set. The highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO) of I, II ve III molecules have been computed and their respective gap (ΔEg) have been examined. The 1H and 13C NMR chemical shift values were calculated in gas phase by GIAO approach using B3LYP/6-311+G (2d,p) and HF/6-31G (d) level of theory. In addition, the potential energy surface (PES) of the molecules as a function of the dihedral angle (C1-C2-B-O1) have been carried out using the 6-31+G basis set in both methods. There are minimums at 0˚, 140˚, 220˚ and 360˚, maximums at 90˚, 180˚ and 270˚ on the calculated potential energy surfaces. The order of the hyperpolarizability values of the molecules is III> II> I. It was seen that I molecule had at the maximum barrier height at 180˚. The dipole moment values of molecules I, IIand IIIare found as 1.18, 1.19 and 1.25 at B3LYP / 6-311++G (d, p) method-basis set combination and 1.17, 1.16 and 1.30 Debye at HF / 6-311++G (d, p) method-basis set combination, respectively. The structural parameters of the Imolecule, which were calculated by both methods, were compared with the data in the literature and there was a good agreement between the structural parameters.

Keywords

2-methoxypyridine, 3-boronic acid, polarizability, HF, DFT / B3LYP, ΔEg

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