DFT CALCULATIONS IN MONOMERIC AND DIMERIC FORMS OF N-BENZYLMALEIMIDE (NBM) COMBINED WITH VIBRATIONAL SPECTROSCOPIC PARAMETERS

Abstract

The structural, vibrational and theoretical analyses of N-benzylmaleimide (NBM) having chemical and biological significances have been made. The four possible conformers and their sixty-six dimeric forms linked by the intermolecular C=O···H hydrogen bonding were investigated for the stability. The conformational and the dimeric structures of NBM in the gas phase were investigated and the population distributions of the conformations and dimers were obtained using the Boltzmann distribution. The experimental IR and Raman spectra of solid phase NBM were recorded, and the bands were compared with the theoretical wavenumber the values of the monomer and the dimer forms for their assignments. The new scale factors (0.9617 for B3LYP/6-31G(d) and 0.9531 for M06-2X/6-31G(d)) obtained for NBM can be used more accurately in vibration calculations of all maleimide derivatives. The Molecular Electrostatic Potential (MEP) map showed that the negative and the positive regions have changed from monomeric to dimeric form changes, while the HOMO-LUMO shapes did not generally change in monomeric and dimeric forms. The nucleophilic and electrophilic Fukui functions and dual descriptors shows that maleimide and benzyl groups are nucleophilic and electrophilic regions, respectively, additionally the dual descriptor values decrease upon dimerization.

Keywords

• N-benzylmaleimide
• dimer
• scale factor
• DFT
• theoretical-vibrational analysis

N-BENZİLMALEİMALEİMİDEDİN (NBM) MONOMERİK VE DİMERİK FORMLARINDA TİTREŞİMSEL SPEKTROSKOPİK PARAMETRELERLE BİRLEŞTİRİLMİŞ DFT HESAPLAMALARI

Abstract

Kimyasal ve biyolojik öneme sahip N-benzilmaleimidin (NBM) yapısal, titreşimsel ve teorik analizleri yapılmıştır. Moleküller arası C=O··H hidrojen bağı ile birbirine bağlanan dört olası konformer ve bunların altmışaltı dimerik formları kararlılık açısından incelenmiştir. NBM'nin gaz fazındaki konformer ve dimer yapılarının Boltzmann dağılımları yoluyla populasyon analizleri yapılıp en kararlı yapı belirlenmiştir. NBM'nin deneysel IR ve Raman spektrumları katı fazda kaydedilmiş ve bu deneysel bantlar molekülünün monomer ve dimer formlarının teorik dalga sayıları ile karşılaştırılıp bantlar yorumlanmıştır. Kullanılan hesaplama yönetemlerinin NBM için bulunan yeni ölçeklendirme faktörleri (B3LYP/6-31G(d) için 0,9617 ve M06-2X/6-31G(d) için 0,9531)) tüm maleimid türevlerinin titreşim frekanslarının hesaplamalarında daha doğru sonuçlar verebileceği görülmüştür. Moleküler Elektrostatik Potansiyel (MEP) haritası, negatif ve pozitif bölgelerin monomerik ve dimerik formlarda değiştiğini, HOMO-LUMO şekillerinin ise monomerik ve dimerik formlarda genelde değişmediğini göstermiştir. Nükleofilik ve elektrofilik Fukui fonksiyonları ve ikili tanımlayıcılar, maleimid grubunun nükleofilik, benzil grubunun ise elektrofilik bölge olduğunu ve ikili tanımlayıcı değerlerin dimerizasyonla azaldığını göstermiştir.

Keywords

• N-benzilmaleimid
• dimer
• scale factor
• DFT
• theoretical-vibrational analysis

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