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

Yıl 2025, Cilt: 15 Sayı: 2, 162 - 183, 31.12.2025

Aslıhan Aycan Tanrıverdi , Ahmet Turan Tekeş , Barış Kartal , Ümit Yıldıko , İsmail Çakmak

https://doi.org/10.37094/adyujsci.1813070

https://izlik.org/JA28KM39ZB

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

https://izlik.org/JA28KM39ZB

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

• [1] Shuaib, N.N., Daud, A.I., Arshad, S., Bakar, M.A.A., Alsaee, S.K and Misnan, N.M., Nonlinear optical (NLO) properties of donor-π-donor featuring diformyltriphenylamine chalcone derivatives, Journal of Molecular Structure, 1327, 141231, 2025.
• [2] Jassas, R.S., Omran, O.A., Abdou, A. et al., Design and DFT calculations of optoelectronic material based on thiazolobenzimidazole-coupled isatin derivatives, Materials Chemistry and Physics, 325, 129689, 2024.
• [3] Xie, L.-H., Yin, C.-R., Lai, W.-Y., Fan, Q.-L., Huang, W., Polyfluorene-based semiconductors combined with various periodic table elements for organic electronics, Progress in Polymer Science, 37, 1192, 2012.
• [4] Jiang, D., Tan, V.G.W., Gong, Y. et al., Semiconducting Covalent Organic Frameworks, Chemical Reviews, 125, 6203, 2025.
• [5] Tommalieh, M.J., Aljameel, A.I., Hussein, R.K., Al-heuseen, K., Alghamdi S.K., and Abu Alrub, S., The Effect of Conjugated Nitrile Structures as Acceptor Moieties on the Photovoltaic Properties of Dye-Sensitized Solar Cells: DFT and TD-DFT Investigation, International Journal of Molecular Sciences, 25, 7138, 2024.
• [6] Nandy, A., Duan, C., Taylor, M.G., Liu, F., Steeves, A.H., Kulik, H.J., Computational Discovery of Transition-metal Complexes: From High-throughput Screening to Machine Learning, Chemical Reviews, 121, 9927, 2021.
• [7] Rybakiewicz, R., Zagorska, M., Pron, A., Triphenylamine-based electroactive compounds: synthesis, properties and application to organic electronics, Chemical Papers, 71, 243, 2017.
• [8] Ahn, M., Kim, M.J., Cho, D.W., Wee., K.R., Electron Push-Pull Effects on Intramolecular Charge Transfer in Perylene-Based Donor-Acceptor Compounds, The Journal of Organic Chemistry, 86, 403, 2021.
• [9] Das, P., Kumar, A., Chowdhury, A., Mukherjee, P.S., Aggregation-Induced Emission and White Luminescence from a Combination of π-Conjugated Donor–Acceptor Organic Luminogens, ACS Omega, 3, 13757, 2018.
• [10] Nowsherwan, G.A., Ali, Q., Ali, U.F., Khan, M., Hussain, S.S., Advances in Organic Materials for Next-Generation Optoelectronics: Potential and Challenges, Organics, 5, 520-560, 2024.
• [11] Nikšić, T., Vretenar, D., Ring, P., Relativistic nuclear energy density functionals: Mean-field and beyond, Progress in Particle and Nuclear Physics, 66, 519-548, 2008.
• [12] Gara, R., Morales-García, Á., Arfaoui, Y., Illas. F., Density Functional Theory (DFT) and Time-Dependent DFT (TDDFT) Studies of Porphyrin Adsorption on Graphene: Insights on the Effect of Substituents and Central Metal on Adsorption Energies, Journal of Computational Chemistry, 46, e27526, 2025.
• [13] Guan, H., Sun, H. and Zhao, X., Application of Density Functional Theory to Molecular Engineering of Pharmaceutical Formulations, International Journal of Molecular Sciences, 26, 3262, 2025.
• [14] Frisch, M., Clemente Scalmani, F., Barone, V., Mennucci, B., Petersson, G.A., Nakatsuji, H., Caricato, M., Li, X., Hratchian, H.P., Izmaylov, A.F., Bloino, J., and Zhe, G., Gaussian 9.
• [15] Stockman, B.J., NMR spectroscopy as a tool for structure-based drug design, Progress in Nuclear Magnetic Resonance Spectroscopy, 33, 109, 1998.
• [16] Yildiko, U., Tanriverdi, A.A., Synthesis and characterization of pyromellitic dianhydride based sulfonated polyimide: Survey of structure properties with DFT and QTAIM, Journal of Polymer Research, 29, 19, 2021.
• [17] Schlegel, H.B., Geometry optimization, WIREs Computational Molecular Science, 1, 790, 2011.
• [18] Yildiko, U., Tanriverdi, A.A., A novel sulfonated aromatic polyimide synthesis and characterization: Energy calculations, QTAIM simulation study of the hydrated structure of one unit, Bulletin of the Korean Chemical Society, 43, 822, 2022.
• [19] Sommer, M., 2 - Development of conjugated polymers for organic flexible electronics, Organic Flexible Electronics, 27-70, 2021.
• [20] Hait, D., Head-Gordon, M., How Accurate Is Density Functional Theory at Predicting Dipole Moments? An Assessment Using a New Database of 200 Benchmark Values, Journal of Chemical Theory and Computation, 14, 1969, 2018.
• [21] Solgun, D.G., Tanriverdi, A.A., Yildiko, U., Ağirtaş. M.S., Synthesis of axially silicon phthalocyanine substituted with bis- (3,4-dimethoxyphenethoxy) groups, DFT and molecular docking studies, Journal of Inclusion Phenomena and Macrocyclic Chemistry, 102, 851, 2022.
• [22] Abdullah, Tanriverdi, A.A., Khan, A.A., et al., Selenium-substituted conjugated small molecule: Synthesis, spectroscopic, computational studies, antioxidant activity, and molecular docking," Journal of Molecular Structure, 1304, 137694, 2024.
• [23] Chen, C., and Fang, C., Fluorescence Modulation by Amines: Mechanistic Insights into Twisted Intramolecular Charge Transfer (TICT) and Beyond, Chemosensors, 11, 87, 2023.
• [24] Puzzarini, C., Barone, V., A never-ending story in the sky: The secrets of chemical evolution, Physics of Life Reviews, 32, 59, 2020.
• [25] Kartal, B., Tanriverdi, A.A., Yildiko, U., Tekes, A.T., Çakmak. I., Polyimide synthesis and characterizations: DFT-assisted computational studies on structural units, Iranian Polymer Journal, 34, 977, 2025.
• [26] Tanriverdi, A.A., Yildiko, U., Tekes, A.T., Cakmak, İ., Ata, A.C., Synthesis, characterization and affinity detection of sulfonated polyimides: confirmation of proton transfer in quantum theory simulations, Polymer Bulletin, 80, 9853, 2023.
• [27] Hadigheh Rezvan, V., Molecular structure, HOMO–LUMO, and NLO studies of some quinoxaline 1,4-dioxide derivatives: Computational (HF and DFT) analysis," Results in Chemistry, 7, 101437, 2024.
• [28] Tanrıverdi, E.A., Tanrıverdi, A.A., Yıldıko, Ü., DFT Calculations, ADME Analysis and Molecular Docking Studies of the Compound AHTPO With the Digestive Enzyme Trypsin Found in Cold-Adapted Fish Species, Sakarya University Journal of Science, 29, 383, 2025.
• [29] Politzer, P., Murray, J.S., Molecular Electrostatic Potentials, ChemInform, 35, 2004.
• [30] Shamina, A.H., Ganesan, V., Jothy, V.B., Manikandan, A., Muthu, S., Javed, S., Quantum chemical computations on molecular composition, spectroscopic properties, topology exploration, NLO, ligand protein interactions and pharmacokinetic evaluation of 8-hydroxyquinolium 3-nitrobenzoate, Chemical Physics Impact, 8, 100394, 2024.