TY - JOUR T1 - A Computational Study of Structural, Electronic, and Nonlinear Optical Properties of Phenylpyrroles AU - Şafak Asar, Yasemin AU - Bahat, Mehmet PY - 2025 DA - June Y2 - 2025 DO - 10.35378/gujs.1532985 JF - Gazi University Journal of Science PB - Gazi University WT - DergiPark SN - 2147-1762 SP - 973 EP - 984 VL - 38 IS - 2 LA - en AB - In this study, three structural isomers of phenylpyrrole:1-, 2-, and 3-phenylpyrrole were investigated by using the B3LYP/6-31++G(d,p) level to get the information about their geometry, electronic and nonlinear optical properties. The change in the torsional angle between the pyrrole and phenyl rings was used to investigate the conformational analysis. In addition, we have calculated the electronic properties such as electric dipole moment, frontier orbital energies and energy gap (E_g). Also, we have determined linear, and nonlinear optical (NLO) properties in terms of polarizability and first hyperpolarizability. KW - Phenylpyrrole KW - B3LYP KW - Conformational analysis KW - Nonlinear optical properties KW - Orbital energy CR - [1] Rettig, W., Marschner, F., "Population of excited charge-transfer states and molecular-conformation in n-phenylpyrroles", Nouveau Journal De Chimie-New Journal of Chemistry, 7: 425-431, (1983). <Go to ISI>://WOS:A1983RF96300005 CR - [2] Sarkar, A., Chakravorti, S., "A Study on the spectroscopy and photophysics of n-phenyl pyrrole and n phenyl pyrazole", Chemical Physics Letters, 235: 195-201, (1995). DOI:https://doi.org/10.1016/0009-2614(95)00111-G CR - [3] Belau, L., Haas, Y., Rettig, W., "Jet cooled spectra of pyrrolobenzene and of pyrrolobenzonitrile:The nature of the excited states", Chemical Physics Letter, 364: 157-163, (2002). DOI:https://doi.org/10.1016/S0009-2614(02)01316-7 CR - [4] Proppe, B., Merchan, M., Serrano-Andres, L., "Theoretical study of the twisted intramolecular charge transfer in 1-phenylpyrrole", Journal of Physical Chemistry A, 104: 1608-1616, (2000). DOI:https://doi.org/10.1021/jp993627g CR - [5] Murali, S., Changenet-Barret, P., Ley, C., Plaza, P., Rettig, W., Martin, M.M., et al., "Photophysical properties of pyrrolobenzenes with different linking and substitution pattern: The transition between charge transfer states with large (MICT) and small (TICT) resonance interaction", Chemical Physics Letter , 411: 192-197, (2005). DOI: https://doi.org/10.1016/j.cplett.2005.06.019 CR - [6] Neubauer, A., Murali, S., Rettig, W., "Charge transfer control by substituents: Donor pyrroles and fluoro anilines", International Journal of Photoenergy, 7: 121-124, (2005). DOI: https://doi.org/10.1155/S1110662x05000188 CR - [7] Schweke, D., Haas, Y., "The fluorescence of n-phenylpyrrole in an argon/acetonitrile matrix", Journal of Physical Chemistry A, 107: 9554-9560, (2003). DOI: https://doi.org/10.1021/jp035959y CR - [8] Zborowski, K., Alkorta, I., Elguero, J., "Substitution effects in phenyl and N-pyrrole derivatives along the periodic table", Structural Chemistry, 18: 797-805, (2007). DOI:https://doi.org/10.1007/s11224007-9245-z CR - [9] Neubauer, A., Bendig, J., Rettig, W., "Control of charge transfer by conformational and electronic effects: Donor-donor and donor-acceptor phenyl pyrroles", Chemical Physics, 358: 235-244, (2009). DOI: https://doi.org/10.1016/j.chemphys.2009.02.008 CR - [10] Santos, A.F.L.O.M., da Silva, M.A.V.R., "Experimental and computational thermochemistry of 1- phenylpyrrole and 1-(4-methylphenyl)pyrrole", Journal of Chemical Thermodynamics, 42: 734-741, (2010). DOI: https://doi.org/10.1016/j.jct.2010.01.009 CR - [11] Santos, A.F.L.O.M., da Silva, M.A.V.R. "Energetics of 1-(aminophenyl) pyrroles: A joint calori- metric and computational study," Journal of Chemical Thermodynamics, 43: 1480-1487, (2011). DOI:https://doi.org/10.1016/j.jct.2011.04.022 CR - [12] Santos, A.F.L.O.M., da Silva, M.A.V.R.," The influence of methyl groups on the torsion angle and on the energetics of 1-phenylpyrrole derivatives: a thermodynamic and computational study", Structural Chemistry, 24: 1981-1992, (2013). DOI: https://doi.org/10.1007/s11224-013-0288-z CR - [13] Galvan, I.F., Martin, M.E., Munoz-Losa, A., Sanchez, M.L., Aguilar, M.A., "Solvent effects on the structure and spectroscopy of the emitting states of 1-phenylpyrrole", Journal of Chemical Theory and Computation, 7: 1850-1857, (2011). DOI: https://doi.org/10.1021/ct2001182 CR - [14] Aleman, C., Domingo, V.M., Julia, L., "A computational study of neutral and charged pyrroles. Functionalization of 1-phenylpyrrole and 2,5-dimethyl-1-phenylpyrrole with electron donating methylsulfanyl groups", Journal of Physical Chemistry A, 105: 5266-5271, (2001). DOI: https://doi.org/DOI10.1021/jp004265b CR - [15] Yoshihara, T., Druzhinin, S.I., Demeter, A., Kocher, N., Stalke, D., Zachariasse, K.A., "Kinetics of intramolecular charge transfer with N-phenylpyrrole in alkyl cyanides", Journal of Physical Chemistry A, 109: 1497-1509, (2005). DOI: https://doi.org/10.1021/jp046586j CR - [16] Pirsa, S., Alizadeh, M., Ghahremannejad, N., "Application of nano-sized poly n-phenyl pyrrole coated polyester fiber to headspace microextraction of some volatile organic compounds and analysis by gas chromatography", Current Analytical Chemistry, 12: 457-464, (2016). DOI:https://doi.org/10.2174/1573411012666151009195422 CR - [17] Tarkuc, S., Sahmetlioglu, E., Tanyeli, C., Akhmedov, I.M., Toppare, L., "A soluble conducting polymer:1-phenyl-2,5-di(2-thienyl)-1H-pyrrole and its electrochromic application", Electrochimica Acta, 51: 5412-5419, (2006). DOI: https://doi.org/10.1016/j.electacta.2006.02.011 CR - [18] Tuzun, N.S., Bayata, F., Sarac, A.S., "An experimental and quantum mechanical study on electrochemical properties of N-substituted pyrroles", Journal of Molecular Structure-Theochem, 857: 95-104, (2008). DOI: https://doi.org/10.1016/j.theochem.2008.02.007 CR - [19] Ayranci, R., Ak, M., "Synthesis of a novel, fluorescent, electroactive and metal ion sensitive thienylpyrrole derivate", New Journal of Chemistry, 40: 8053-8059, (2016). DOI:https://doi.org/10.1039/c6nj02006b CR - [20] Carbas, B.B., Ergin, N.M., Yildiz, H.B., Kivrak, A., Demet, A.E., "Electrochromic properties of a polydithienylpyrrole derivative with N-phenyl pyrrole subunit", Materials Chemistry and Physics, 293: 1-9, (2023). DOI:https://doi.org/10.1016/j.matchemphys.2022.126916 CR - [21] Sarac, A.S., Sezgin, S., Ates, M., Turhan, C.M., "Electrochemical impedance spectroscopy and morphological analyses of pyrrole, phenylpyrrole and methoxyphenylpyrrole on carbon fiber microelectrodes", Surface & Coatings Technology, 202: 3997-4005, (2008). DOI: https://doi.org/10.1016/j.surfcoat.2008.02.007 CR - [22] Liu, F.G., Wang, H.R., Yang, Y.H., Xu, H.J., Zhang, M.L., Zhang, A.R., et al., "Nonlinear optical chromophores containing a novel pyrrole-based bridge: optimization of electro-optic activity and thermal stability by modifying the bridge", Journal of Materials Chemistry C, 2: 7785-7795, (2014). DOI: https://doi.org/10.1039/c4tc00900b CR - [23] Peterson, B.N., Alfieri, M.E., Hood, D.J., Hettwer, C.D., Costantino, D.V., Tabor, D.P., et al., "Solvent-mediated charge transfer dynamics of a model brown carbon aerosol chromophore: Photophysics of 1-phenylpyrrole induced by water solvation", Journal of Physical Chemistry A, 126: 4313-4325, (2022). DOI: https://doi.org/10.1021/acs.jpca.2c00585 CR - [24] Figueira, C.A., Lopes, P.S., Gomes, C.S.B., Veiros, L.F., Gomes, P.T., "Exploring the influence of steric hindrance and electronic nature of substituents in the supramolecular arrangements of 5 (substituted phenyl)-2-formylpyrroles", Crystengcomm, 17: 6406-6419, (2015). DOI:https://doi.org/10.1039/c5ce00927h CR - [25] Jones, T.H., Flournoy, R.C., Torres, J.A., Snelling, R.R., Spande, T.F., Garraffo, H.M., "3-Methyl- 4- phenylpyrrole from the Ants Anochetus kempfi and Anochetus mayri", Journal of Natural Products, 62: 1343-1345, (1999). DOI: https://doi.org/10.1021/np990245t CR - [26] Brandhorst, T.T., Kean, I.R.L., Lawry, S.M., Wiesner, D.L., Klein, B.S., "Phenylpyrrole fungicides act on triosephosphate isomerase to induce methylglyoxal stress and alter hybrid histidine kinase activity", Scientific Reports, 9, (2019). DOI: https://doi.org/10.1038/s41598-019-41564-9 CR - [27] Kilani, J., Fillinger, S., "Phenylpyrroles: 30 Years, two molecules and (nearly) resistance", Frontiers in Microbiology, 7, (2016). DOI: https://doi.org/10.3389/fmicb.2016.02014 CR - [28] Biswas, N., Ghosh, S., Bag, A., "p-di-pyrrole Benzene derivatives - A new class of highly active HIV-1CA inhibitors", Acta Scientific Pharmaceutical Sciences, 5: 92-100, (2021). CR - [29] Meindl, K., Henn, J., Kocher, N., Leusser, D., Zachariasse, K.A., Sheldrick, G.M., et al., "Experimental charge density studies of disordered n-phenylpyrrole and n-(4-fluorophenyl)pyrrole", Journal of Physical Chemistry A, 113: 9684-9691, (2009). DOI:https://doi.org/10.1021/jp9026157 CR - [30] Okuyama, K., Numata, Y., Odawara, S., Suzuka, I., "Electronic spectra of jet-cooled 1 phenylpyrrole: Large-amplitude torsional motion and twisted intramolecular charge-transfer phenomenon", Journal of Chemical Physics, 109: 7185-7196, (1998). DOI:https://doi.org/10.1063/1.477355 CR - [31] Trofimov, B.A., Stepanova, Z.V., Sobenina, L.N., Mikhaleva, A.I., Sinegovskaya, L.M., Potekhin, K.A., et al., "2-(2-Benzoylethynyl)-5-phenylpyrrole: fixation of cis- and trans-rotamers in a crystal state", Mendeleev Communications, 15: 229-32, (2005). DOI:https://doi.org/10.1070/MC2005v015n06ABEH002190 CR - [32] Galasso, V., De Alti, G., "MO calculations on the preferred conformation and electronic structure of phenyl-derivatives of pyrrole, furan and thiophene", Tetrahedron, 27: 4947-51, (1971). DOI:https://doi.org/10.1016/S0040-4020(01)98200-6 CR - [33] Fabian, W., "Conformational behavior of phenylpyrroles - A semiempirical molecular-orbital study", Zeitschrift Fur Naturforschung Section A-A Journal of Physical Sciences, 42: 641-4, (1987). DOI:https://doi.org/DOI 10.1515/zna-1987-0621 CR - [34] Rottmannova, L., Punyain, K., Rimarcik, J., Lukes, V., Klein, E., Kelterer, A.M., "Theoretical study of 2-phenylpyrrole molecule using various quantum-chemical approaches", Acta Chimica Slovaca, 5: 21-8, (2012). DOI: https://doi.org/10.2478/v10188-012-0004-4 CR - [35] Lumbroso, H., Bertin, D.M., Marschner, F., "A dipole-moment study on gradually hindered N phenylpyrroles", Journal of Molecular Structure, 178: 187-200, (1988). DOI:https://doi.org/10.1016/0022-2860(88)85017-8 CR - [36] Thomas, J.A., Young, J.W., Fleisher, A.J., Alvarez-Valtierra, L., Pratt, D.W., "Stark-effect studies of 1-phenylpyrrole in the gas phase. Dipole reversal upon electronic excitation", Journal of Physical Chemistry Letters, 1: 2017-9, (2010). DOI: https://doi.org/10.1021/jz100653j CR - [37] Ghiasi, R., Rahimi, M., Siavoshani, A.Y., "Stability, electronic and optical properties of irida- naphthalene and irida-azulene: A computational investigation", Russian Journal of Physical Chemistry A, 97: 2189-97, (2023). DOI: https://doi.org/10.1134/S0036024423100187 CR - [38] Ghiasi, R., Pasdar, H., "Computational study of substituent effect in para substituted platinabenzene complexes", Russian Journal of Physical Chemistry A, 87: 973-8, (2013). DOI:https://doi.org/10.1134/S0036024413060368 CR - [39] Becke, A.D., "Density-functional thermochemistry .3. The role of exact exchange", Journal of Chemical Physics, 98: 5648-5652, (1993). DOI: https://doi.org/Doi 10.1063/1.464913 CR - [40] Lee, C.T., Yang, W.T., Parr, R.G., "Development of the Colle-Salvetti correlation-energy formula into a functional of the electron-density", Physical Review B, 37: 785-789, (1988). DOI: https://doi.org/10.1103/PhysRevB.37.785 CR - [41] Hariharan, P.C., Pople, J.A., "Influence of polarization functions on molecular-orbital hydrogenation energies", Theoretical Chemistry Accounts, 28: 213-222, (1973). DOI:https://doi.org/10.1007/BF00533485 CR - [42] Ditchfield, R., Hehre, W.J., and , Pople, J.A., "Self-consistent molecular orbital methods. 9. Extended Gaussian-type basis for molecular-orbital studies of organic molecules", Journal of Chemical Physics, 54: (1971). DOI: https://doi.org/10.1063/1.1674902 CR - [43] Frisch, M.J., Frisch, M., Trucks, G., Schlegel, K., Scuseria, G., Robb, M., et al., Gaussian 03, Revision C.02, Gaussian, Inc., Pittsburgh, PA,. (2003). CR - [44] Sert, Y., El-Hiti, G.A., Gökce, H., Ucun, F., Abdel-Wahab, B.F., Kariuki, B.M., "DFT, molecular docking and experimental FT-IR, laser-raman, NMR and UV investigations on a potential anticancer agent containing triazole ring system", Journal of Molecular Structure, 1211, (2020). DOI: https://doi.org/10.1016/j.molstruc.2020.128077 CR - [45] Sakr, M.A.S., Mohamed, A.A., Abou Kana, M.T.H., Elwahy, A.H.M., El-Daly, S.A., Ebeid, E.Z.M., "Synthesis, characterization, DFT and TD-DFT study of novel bis(5,6-diphenyl-1,2,4-triazines) ", Journal of Molecular Structure, 1226, (2021). DOI:https://doi.org/10.1016/j.molstruc.2020.129345 CR - [46] Hadji, D., Champagne, B., "First Principles Investigation of the Polazirability and First Hyper polarizability of Anhyride Derivatives", Chemistry Africa, 2: 443-53, (2019). DOI:https://doi.org/10.1007/s42250-019-00060-3 CR - [47] Olejniczak, M., Pecul, M., Champagne, B., Botek, E., "Theoretical investigation on the linear and nonlinear susceptibilities of urea crystal", Journal of Chemical Physics, 128, (2008). DOI:https://doi.org/10.1063/1.2938376 CR - [48] Adant, C., Dupuis, M., Bredas, J.L., "Ab-Initio study of the nonlinear-optical properties of urea – Electron correlation and dispersion effects", International Journal of Quantum Chemistry, 56 (S29): 497-507, (1995). UR - https://doi.org/10.35378/gujs.1532985 L1 - https://dergipark.org.tr/en/download/article-file/4143980 ER -