Physical Chemistry Research

Enhanced Switching Behavior of (Z)-2-Phenyl-4-((phenylamino)methylene)-5-(trifluoromethyl)-2,4-dihydro-3H-pyrazol-3-one Driven by Hydrogen Transfer

Document Type : Special issue in the honor of Prof. Pakiari

Authors

Vahidreza Darugar 1
Mahmood Akbari 2
Fatemeh Shahin 3

1 Department of Chemistry, Faculty of Science, Ferdowsi University of Mashhad, Iran

2 UNESCO-UNISA-ITL/NRF Africa Chair in Nanoscience & Nanotechnology (U2ACN2), College of Graduate Studies, University of South Africa (UNISA), Pretoria, South Africa

3 Department of Science, Isfahan (Khorasgan) Branch, Islamic Azad University, Isfahan P.O. Box: 81595-158, Iran

https://doi.org/10.22036/pcr.2025.494643.2608
Abstract
An innovative molecular switch, (Z)-2-phenyl-4-((phenylamino)methylene)-5-(trifluoromethyl)2,4-dihydro-3H-pyrazol-3-one, was theoretically designed and evaluated for its switching behavior using density functional theory (DFT) and nonequilibrium Green's function (NEGF) methods. Both the -NH and -OH tautomeric forms of the molecule were investigated. At the DFT-B3LYP/6-311++G** level, the -OH form exhibited a significantly stronger intramolecular hydrogen bond (13.5 kcal/mol) compared to the -NH form (7.0 kcal/mol). The molecular conductance was analyzed across silver, platinum, and gold electrodes, considering different adsorption sites (top, hollow, and bridge), through I-V characteristics, on/off ratios, transmittance spectra, and projected density of states (PDOS). A distinct transition from high to low resistance was observed upon switching from the -NH to the -OH form, confirming effective molecular switching behavior. Notably, the hollow site on the gold surface provided the highest switching efficiency. These results underscore the promise of this molecule as a candidate for next-generation molecular electronic and photonic devices.

Graphical Abstract

Enhanced Switching Behavior of (Z)-2-Phenyl-4-((phenylamino)methylene)-5-(trifluoromethyl)-2,4-dihydro-3H-pyrazol-3-one Driven by Hydrogen Transfer

Keywords

(Z)-2-Phenyl-4-((phenylamino)methylene)-5-(triflouromethyl)2
4-dihydro-3H-pyrazol-3-one
Switching potent
Current-voltage
PDOS
IHB

Subjects

[1] Venkataraman, L.; Klare, J. E.; Nuckolls, C.; Hybertsen, M. S.; Steigerwald, M. L., Dependence of single-molecule junction conductance on molecular conformation. Nature 2006, 442, 904-907. DOI: 10.1038/nature05037.
[2] Correa-Duarte, M. A.; Wagner, N.; Rojas-Chapana, J.; Morsczeck, C.; Thie, M.; Giersig, M., Fabrication and biocompatibility of carbon nanotube-based 3D networks as scaffolds for cell seeding and growth. Nano Lett. 2004, 4, 2233-2236. DOI: 10.1021/nl048574f.
[3] Guo, X.; Small, J. P.; Klare, J. E.; Wang, Y.; Purewal, M. S.; Tam, I. W.; Nuckolls, C., Covalently bridging gaps in single-walled carbon nanotubes with conducting molecules. Science 2006, 311, 356-359. DOI: 10.1126/science.1120986.
[4] Saidi, F.; Dergal, M.; Dendane, A.; Ameur, N., First-principles investigation of structural stability, electronic, and optical properties of V, Y-Doped, and (V, Y)-codoped monoclinic ZrO2. Phys. Chem. Res. 2024, 12, 663-674. DOI: 10.22036/pcr.2023.416669.2419.
[5] Chen, J.; Reed, M. A.; Rawlett, A. M.;  Tour, J. M., Large on-off ratios and negative differential resistance in a molecular electronic device. Science 1999, 286, 1550-1552. DOI: 10.1126/science.286.5444.1550.
[6] Khosravi, E.; Stefanucci, G.; Kurth, S.; Gross, E. K. U., Bound states in time-dependent quantum transport: oscillations and memory effects in current and density. Phys. Chem. Chem. Phys. 2009, 11, 4535-4538. DOI: 10.1039/B906528H.
[7] Vakili, M.; Sobhkhizi, A.; Darugar, V.; Kanaani, A.; Ajloo, D., A first-principles study of aryloxyanthraquinone-based optical molecular switch. Chem. Phys. Lett. 2017, 686, 140-147. DOI: 10.1016/j.cplett.2017.08.045.
[8] Kanaani, A.; Vakili; M.;  Ajloo, D., Electronic transport properties of 2-nIiitro-4-(6-(4-nitrophenyl)-4-phenyl-1, 3-diaza-bicyclo [3.1. 0] hex-3-en-2-yl) phenol: A light-driven molecular switch. Optik 2020,  219, 165295. DOI: 10.1016/j.ijleo.2020.165295.
[9] Darugar, V.; Vakili, M.; Tayyari, S. F., Electronic transport behavior of 1-(Phenyldiazenyl) naphthalen-2-ol and its derivatives as optical molecular switches: A first-principles approach. Optik 2021, 236, 166475. DOI: 10.1016/j.ijleo.2021.166475.
[10] Darugar, V.; Vakili, M.; Tayyari S. F., Voltage–current behavior of 4-phenylamino-3-penten-2-one and its derivatives molecular switch: a first-principles study. Mol. Simul. 2021, 47, 730-737. DOI: 10.1080/ 08927022.2021.1917767.
[11] Darugar, V.; Vakili, M.;  Brandán, S. A., Electrical transport and NDR property on the cis–trans photo-isomerization of (1R, 3S)-2,2-dimethyl-3-(2-methylprop-1-en-1-yl) cyclopropanecarboxylate as an optical molecular switch; A DFT-NEGF study. Chem. Phys. Lett. 2022, 803, 139818. DOI: 10.1016/ j.cplett.2022.139818.
[12] Darugar, V.; Vakili, M.; Tahriri, M.; Berenji, A. R.; Nekoei, A. R.; Kanaani, A., First-principle study on the conductance performance of Salicylidene Ethylamine molecular optical switch and its alkyl halide derivatives. Opti. Quantum Electon. 2022, 54, 542. DOI: 10.1007/s11082-022-03929-9.[13] Aliabadi, M. E.; Vakili, M.; Kanaani, A.; Darugar, V.; Seyedkatouli, S., First-principle study of the current–voltage on the β-diketones with alkyl and methoxy groups at the beta position as molecular switches. Chem. Phys. Lett. 2022, 809, 140152. DOI: 10.1016/ j.cplett.2022.140152.
[14] Darugar, V.; Vakili, M.; Brandan, S. A.; Adli, S., Electronic transport on the two state “ON–OFF” of 1,3, 3-trimethylindolino-6′-nitrobenzopyrylospiran as a light-driven molecular optical switch: A first-principle study. J. Mol. Graph. Model. 2023, 120, 108420. DOI: 10.1016/j.jmgm.2023.108420.
[15] Zhou, Y. -H.; Zheng, X. -H.; Zeng, Z. Y.; Xu, Y., Current rectification by asymmetric molecules: An ab initio study, J. Chem. Phys. 2006, 125, 244701. DOI: 10.1063/1.2409689.
[16] Xia, C. J.; Chen, A. M.; Zhang, Y. T., Effect of carbon nanotubes chirality on the E–C photo-isomerization switching behavior in moelcular device. Optik 2014, 125, 4522-4525. DOI: 10.1016/j.ijleo.2014.02.015.
[17] Jiang, F.; Zhou, Y. X.; Chen, H.; Note, R.; Mizuseki, H.; Kawazoe, Y., First-principles study of phenyl ethylene oligomers as current-switch. Phys. Lett. A 2006, 359, 487-493. DOI: 10.1016/j.physleta.2006.06.070.
[18] Liao, J.; Agustsson, J. S.; Wu, S.; Schönenberger, C.; Calame, M.; Leroux, Y.; Decurtins, S., Cyclic conductance switching in networks of redox-active molecular junctions. Nano lett.  2010, 10, 759-764. DOI: 10.1021/nl902000e.
[19] Chen, F.; He, J.; Nuckolls, C.; Roberts, T.; Klare, J. E.; Lindsay, S., A molecular switch based on potential-induced changes of oxidation state. Nano Lett. 2005, 5, 503-506. DOI: 10.1021/nl0478474.
 [20] a) Negri, G.; Kascheres, C.; Kascheres, A. J., Recent development in preparation reactivity and biological activity of enaminoketones and enaminothiones and their utilization to prepare heterocyclic compounds. J. Heterocyclic Chem. 2004, 41, 461-491. DOI: 10.1002/jhet.5570410402. b) AElassar, A. Z. A.; El-Khair, A. A., Recent developments in the chemistry of enaminones. Tetrahedron, 2003, 59, 8463-8480. DOI: 10.1016/S0040-4020(03)01201-8. c) Cacchi, S.; Fabrizi, G.; Filisti, E., N-propargylic β-enaminones: Common intermediates for the synthesis of polysubstituted pyrroles and pyridines. Org. Lett. 2008, 10, 2629-2632. DOI: 10.1021/ol800518j d) Saito, A.; Konishi, T.; Hanzawa, Y., Synthesis of pyrroles by gold (I)-catalyzed amino-Claisen rearrangement of N-propargyl enaminone derivatives. Org. Lett. 2010, 12, 372-374. DOI:  10.1021/ol902716n.e) Goutham, K.; Ashok Kumar, D.; Suresh, S.; Sridhar, B.; Narender, R.; Karunakar, G. V., Gold-catalyzed intramolecular cyclization of N-propargylic β-enaminones for the synthesis of 1,4-oxazepine derivatives. J. Org. Chem.  2015, 80, 11162-11168. DOI: 10.1021/acs.joc.5b01733.
[21] El-Sabbagh, O. I.; Rady, H. M., Synthesis of new acridines and hydrazones derived from cyclic β-diketone for cytotoxic and antiviral evaluation. Europ. J. Medicinal Chem. 2009, 44, 3680-3686. DOI: 10.1016/j.ejmech.2009.04.001.
[22] Wolfbeis, O. S., Eine effiziente Synthese von Aminoalkylidenderivaten fünfringcyclischer methylenaktiver Verbindungen. Monatshefte für Chemie/Chemical Monthly, 1981, 112, 369-383. DOI: 10.1007/BF00900767.
[23] Raeisian, M.; Izadi, M. E.; Ajloo, D., Experimental and Theoretical Study of Cis-1,4-polyisoprene Pyrolysis. Phys. Chem. Res. 2025, 13, 115-127. DOI: 10.22036/ pcr.2024.448894.2503.
[24] a) Jezierska, A.; Jerzykiewicz, L. B.; Kołodziejczak, J.; Sobczak, J. M., Synthesis, X-ray crystal structure and DFT study of potential ligands of (2Z)-3-[(2-hydroxyphenyl) amino]-1-phenyl” alk”-2-en-1-one type. J. Mol. Struct. 2007, 839, 33-40 DOI: 10.1016/j.molstruc.2006.11.006. b) Parekh, B. B.; Purohit, D. H.; Sagayaraj, P.; Joshi, H. S.; Joshi, M. J., Growth and characterization of 4‐(2‐hydroxyphenylamino)‐pent‐3‐en‐2‐one single crystals. Crystal Res. and Tech. J. Exp. Indust. Crystallography 2007, 42, 407-415. DOI: 10.1002/crat.200610836 c) Kabak, M.; Elmali, A.; Elerman, Y., Tautomeric properties, conformations and structure of N-(2-hydroxyphenyl)-4-amino-3-penten-2-on. J. Mol.          Struct.  1998, 470, 295-300. DOI: 10.1016/S0022-2860(98)00377-9.
[25] Ogawa, K.; Harada, J.; Fujiwara, T.; Yoshida, S., Thermochromism of salicylideneanilines in solution: aggregation-controlled proton tautomerization. J. Phys. Chem. A 2001, 105, 3425-3427. DOI: 10.1021/ jp003985f.
[26] Tayyari, S. F.; Ghafari, M.; Jamialahmadi, M.; Chahkandi, B.; Patrick, B. O.; Wang, Y. A., Vibrational assignment and crystal structure of 3-amino-1-phenyl-2-buten-1-one. J. Mol. Struct. 2013, 1045, 20-28. DOI: 10.1016/j.molstruc.2013.04.029.
[27] Soltani-Ghoshkhaneh, S.; Vakili, M.; Berenji, A. R.; Darugar, V.; Tayyari, S. F., Conformations, molecular structure, and N–H⋯ O hydrogen bond strength in 4-Alkylamino-3-penten-2-ones. J. Mol. Struct. 2020, 1203, 127440. DOI: 10.1016/j.molstruc.2019.127440.
[28] Frisch, M. J. et al., 2009, Gaussian 09, Revision d. 01, Gaussian. Inc, Wallingford CT, 201.
[29] Biegler, K. F.; Schnbohm, J.; Bayles, D., 2001, AIM200, A program to analyze and visualize atoms in molecules.
[30] Cao, Y.; Ge, Q.; Dyer, D. J.; Wang, L., Steric effects on the adsorption of alkylthiolate self-assembled monolayers on Au (111).  J. Phys. Chem. B 2003, 107, 3803-3807. DOI: 10.1021/jp021989+.
[31] Sellers, H.; Ulman, A.; Shnidman, Y.;  Eilers, J. E., Structure and binding of alkanethiolates on gold and silver surfaces: implications for self-assembled monolayers. J. Am. Chem. Soc. 1993, 115, 9389-9401. DOI: 10.1021/ja00074a004.
[32] Geng, W. T.; Nara, J.; Ohno, T., Adsorption of benzene thiolate on the (111) surface of M (M=Pt, Ag, Cu) and the conductance of M/benzene dithiolate/M molecular junctions: a first-principles study. Thin Solid Films, 2004, 464, 379-383. DOI: 10.1016/j.tsf.2004.06.083.
[33] Kondo, H.; Nara, J.; Kino, H.; Ohno, T., Transport properties of a biphenyl-based molecular junction system the electrode metaldependence. J. Phys.: Cond. Matter, 2009, 21, 064220. DOI: 10.1088/0953-8984/21/6/064220.
[34] Kanaani, A.; Ajloo, D.; Kiyani, H.; Shaheri, F.; Amiri, M., Synthesis, molecular structure, spectroscopic investigations and computational study of a potential molecular switch of 2-([1,1’-biphenyl]-4-yl)-2-methyl-6-(4-nitrophenyl)-4-phenyl-1, 3 diazabicyclo [3.1. 0] hex-3-ene. J. Chem. Sci. 2016, 128, 1211-1221. DOI: 10.1007/s12039-016-1118-9.
[35] Kanaani, A.; Ajloo, D.; Kiyani, H.; Ghasemian, H.; Vakili, M.; Feizabadi, M., Molecular structure, spectroscopic investigations and computational study on the potential molecular switch of (E)-1-(4-(2-hydroxybenzylideneamino) phenyl) ethanone. Mol. Phys. 2016, 114, 2081-2097. DOI: 10.1080/ 00268976.2016.1178822.
[36] Gottschalck, J.; Hammer, B., A density functional theory study of the adsorption of sulfur, mercapto, and methylthiolate on Au (111).  J. Chem. Phys.  2002, 116, 784-790. DOI: 10.1063/1.1424292.
[37] Kondoh, H.; Iwasaki, M.; Shimada, T.; Amemiya, K.; Yokoyama, T.; Ohta, T.; Kono, S., Adsorption of Thiolates to Singly Coordinated Sites on Au (111) Evidenced by Photoelectron Diffraction. Phys. Rev. Lett. 2003, 90, 066102. DOI: 10.1103/ PhysRevLett.90.066102.
[38] Jiang, Z.; Li, M.; Yan, T.; Fang, T., Decomposition of H2O on clean and oxygen-covered Au (1 0 0) surface: A DFT study. Appl.Surf. Sci. 2014, 315, 16-21. DOI: 10.1016/j.apsusc.2014.07.076.
[39] Rodriguez, J. A.; Hrbek, J.; Kuhn, M.; Jirsak, T.; Chaturvedi, S.; Maiti, A., Interaction of sulfur with Pt (111) and Sn/Pt (111): effects of coverage and metal–metal bonding on reactivity toward sulfur. J. Chem. Phys. 2000, 113, 11284-11292. DOI: 10.1063/ 1.1327249.
[40] Ma, S. H.; Jiao, Z. Y.; Yang, Z. X., Coverage effects on the adsorption of sulfur on Co (0 0 0 1): A DFT study. Surf. Sci. 2010, 604, 817-823. DOI: 10.1016/ j.susc.2010.02.006.
[41] Martorell, B.; Clotet, A.; Fraxedas, J., A first principle study of the structural, vibrational and electronic properties of tetrathiafulvalene adsorbed on Ag (110) and Au (110) surfaces. J. Comput. Chem. 2010, 31, 1842-1852. DOI: 10.1002/jcc.21465.
[42] Seitsonen, A. P.; Zhu, Y.; Bedürftig, K.; Over, H., Bonding mechanism and atomic geometry of an ordered hydroxyl overlayer on Pt (111). J. Am. Chem. Soc. 2001, 123, 7347-7351. DOI: 10.1021/ja015525l.
[43] Persson, I.; Nilsson, K. B., Coordination Chemistry of the solvated Silver(I) Ion in the oxygen donor           solvents water, dimethyl sulfoxide, and N,N‘-Dimethylpropyleneurea. Inorg. Chem. 2006, 45, 7428-7434. DOI: 10.1021/ic060636c.
 [44] Zhao, P.; Liu, D. S.; Xie, S. J., Ab initio investigation of the I–V characteristics of the phenoxynaphthacenequinone-based optical molecular switch. Phys. Lett. A 2008, 372, 5811-5815. DOI: 10.1016/j.physleta.2008.07.014.
[45] Das, B.; Abe, S.; Naitoh, Y.; Horikawa, M.; Yatabe, T.; Suzuki, Y.; Kawanishi, Y., Modeling and testing of molecular wire sensors to detect a nucleic acid base. J. Phys. Chem. C 2007, 111, 3495-3504. DOI: 10.1021/ jp0659709.
[46] Staykov, A.; Nozaki, D.; Yoshizawa, K., Photoswitching of conductivity through a diarylperfluorocyclopentene nanowire. J. Phys. Chem. C 2007, 111, 3517-3521. DOI: 10.1021/jp067612b.
[47] Brandbyge, M.; Mozos, J. L.; Ordejón, P.; Taylor, J.; Stokbro, K., Density-functional method for nonequilibrium electron transport. Phys. Rev. B, 2002, 65, 165401. DOI: 10.1103/PhysRevB.65.165401.
[48] Perdew, J. P.; Burke, K.; Ernzerhof, M., Generalized gradient approximation made simple. Phys. Rev. Lett., 1996, 77, 3865. DOI: 10.1103/PhysRevLett.77.3865.
[49] Sayyar, Z.; Vakili, M.; Kanaani, A.; Eshghi, H., First-principles study of 2,6-dimethyl-3,5-heptanedione: a β-diketone molecular switch induced by hydrogen transfer. J. Comput. Electronics, 2020, 19, 917-930. DOI: 10.1007/s10825-020-01525-2.
[50] Seyedkatouli, S.; Vakili, M., Current–voltage characteristics of β-ketoenamines molecular switches induced by intramolecular hydrogen transfer. Indian J. Phys. 2019, 93, 1527-1535. DOI: 10.1007/s12648-019-01420-y.
[51] Ganji, M. D.; Mir-Hashemi, A., Ab initio investigation of the I–V characteristics of the butadiene nano-molecular wires: A light-driven molecular switch. Phys. Lett. A 2008, 372, 3058-3063. DOI: 10.1016/ j.physleta.2008.01.025.
[52] Laskar, R. A.; Begum, N. A.; Mir, M. H.; Ali, S.; Khan, A. T., Vanadium(IV) acetylacetonate catalyzed stereoselective synthesis of β-enaminoesters and β-enaminones. Tetrahedron Lett. 2013, 54, 436-440. DOI: 10.1016/j.tetlet.2012.11.051.
[53] Nowroozi, A.; Raissi, H.; Farzad, F., The presentation of an approach for estimating the intramolecular hydrogen bond strength in conformational study of β-Aminoacrolein. J. Mol. Struct.: THEOCHEM, 2005, 730, 161-169. DOI: 10.1016/j.theochem.2005.04.018. 
[54] Espinosa, E.; Molins, E.; Lecomte, C., Hydrogen bond strengths revealed by topological analyses of experimentally observed electron densities. Chem. Phys. Llett. 1998, 285, 170-173. DOI: 10.1016/S0009-2614(98)00036-0.
[55] Marsella, M. J.; Wang, Z. Q.; Mitchell, R. H., Backbone photochromic polymers containing the dimethyl-dihydropyrene moiety: Toward optoelectronic switches. Org. Lett. 2000, 2, 2979-2982. DOI: 10.1021/ol006293i
[56] Datta, S., 1997, Electronic transport in mesoscopic systems. Cambridge university press.
[57] Staykov, A.; Nozaki, D.; Yoshizawa, K., Theoretical study of donor− π-bridge− acceptor unimolecular electric rectifier. J. Phys. Chem. C, 2007, 111, 11699-11705. DOI: 10.1021/jp072600r.
Physical Chemistry Research
Volume 13, Issue 4
Autumn 2025
Pages 631-642

  • Receive Date 18 December 2024
  • Revise Date 28 May 2025
  • Accept Date 13 July 2025