Published Aug 27, 2018


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Ximena Verónica Jaramillo-Fierro

César Zambrano

Francisco Fernández

Regino Saenz-Puche

César Costa

Victor Guerrero

Silvia González



A new Cu(I) complex constructed by reaction of trithiocyanuric acid (ttc) and copper (II) perchlorate hexahydrate has been successfully synthesized by a slow sedimentation method in a DMF solvent at room temperature. The molecular structure of the compound was elucidated by MALDI-TOFMS, UV Vis and FTIR spectroscopy, DSC-TGA analysis and magnetic susceptibility measurement. The proposed structure was corroborated by a computational study carried out with the Gaussian09 and AIMAII programs using the RB3LYP hybrid DFT functional with both 6-31G and Alhrich-TZV basis sets. The calculated vibrational frequencies values were compared with experimental FTIR values. Photophysical properties of the synthesized complex were evaluated by UV-Visible spectroscopy and compared with computed vertical excitation obtained from TDDFT. The theoretical vibrational frequencies and the UV Vis spectra are in good agreement with the experimental values. Additionally, the Frontier Molecular Orbitals (HOMO-LUMO) and the Molecular Electrostatic Potential of the complex was calculated using same theoretical approximation. The results showed the interaction between three coordinatedl igand atoms and the Cu(I) ion.


coordination complex, copper perchlorate, trithiocyanuric acid, DFT calculations

[1] Morsali A, Masoomi MY. Structures and properties of mercury(II) coordination polymers. Coordination Chemistry Reviews, 253(13-14): 1882-1905, 2009.
doi: 10.1016/j.ccr.2009.02.018

[2] Li XM, Wang QW, Zhan PY, Pan YR. Synthesis, Crystal Structure and Theoretical Calculations of a Cadmium(II)
Coordination Polymer Assembled by 4, 4′-Oxydibenzoic Acid and 1,3-Bis(imidazol-1-ylmethyl)-Benzene Ligands, Journal of Chemical Crystallography, 46(4): 163-169, 2016.
doi: 10.1007/s10870-016-0641-3

[3] Otieno T, Hutchison AR, Krepps MK, Atwood DA. Synthesis and Spectral and Thermal Properties of Pyrazine-Bridged Coordination Polymers of Copper (II) Nitrate An Experiment for Advanced Undergraduates, Journal of Chemical Education, 79(11): 1355-1357, 2002.
doi: 10.1021/ed079p1355

[4] Kope P, et al. Ferromagnetic Properties of a Trinuclear Nickel(II) Complex with a Trithiocyanurate Bridge, European Journal of Inorganic Chemistry, 36: 5475-5482, 2009.
doi: 10.1002/ejic.200900617

[5] Brito I, Albanez J, Bolte M. Trithiocyanuric acid: a second triclinic polymorph, Crystallographic Communications, 66(9): 2382-2383, 2010.
doi: 10.1107/S1600536810033234

[6] Yin X, Jin X, Xu CX, He P, Wang K, Zhang G. Synthesis and characterization of four energetic transition metal complexes of 3,4-diamino-1,2,4-triazole, Central European Journal of Energetic
Materials, 13(2): 301-320, 2016.
doi: 10.22211/cejem/64985

[7] Kopel P, Trávníček’Z, Kvítek L, Černošek Z, Wrzeszcz G, Marek J. Synthesis and Characterization of Cu(II), Co(II) and Ni(II) Complexes of Trithiocyanuric Acid: The Structure of {N,N′-Bis(3-Aminopropyl)-1,3-Propanediamine}-(Trithiocyanurato) Nickel(II), Journal of Coordination Chemistry, 56(1): 1-11, 2003.
doi: 10.1080/0095897021000039034

[8] Simonot L, Hébert M, Dupraz D. Goniocolorimetry: From measurement to representation in the CIELAB color space, Color Research Application, 36(2): 169-178, 2010.
doi: 10.1002/COL.20605

[9] Thulstrup PW, Larsen E. The electronic structure and spectra of spin-triplet ground state bis(biuretato)cobalt(III) coordination compounds, Dalton Transactions, 12(14): 1784, 2006.
doi: 10.1039/b513571k

[10] Tretyakov EV, et al. Method for the synthesis of a stable heteroatom analog of trimethylenemethane, Russian Chemical Bulletin, 60(12): 2608-2612, 2011.
doi: 10.1007/s11172-011-0400-8

[11] Wurzenberger X, Piotrowski H, Klüfers P. A Stable Molecular Entity Derived from Rate Iron(II) Minerals: The Square- Planar High-Spin-d6 FeIIO4 Chromophore. Angewandte Chemie International Edition, 50(21): 4974-4978, 2011.
doi: 10.1002/anie.201006898

[12] Domratcheva T, Schlichting I. Electronic Structure of (6-4) DNA Photoproduct Repair Involving a Non-Oxetane Pathway, Journal of the American Chemical Society, 131(49): 17793-17799,
doi: 10.1021/ja904550d

[13] Pietrzyk P, Srebro M, Radón M, Sojka Z, Michalak A. Spin Ground State and Magnetic Properties of Cobalt(II): Relativistic DFT Calculations Guided by EPR Measurements of Bis(2.4-acetylacetonate)cobalt(II)-Based Complexes, Journal Physical Chemistry A, 115(11): 2316-2324, 2011.
doi: 10.1021/jp109524t

[14] Abdel-Rahman LH, Abu-Dief AM, Adam MSS, Hamda SK. Some New Nano-sized Mononuclear Cu(II) Schiff Base Complexes: Design, Characterization, Molecular Modeling and Catalytic Potentials in Benzyl Alcohol Oxidation, Catalysis Letters, 146: 1373-1396, 2016.
doi: 10.1007/s10562-016-1755-0

[15] Abdel-Rahman LH, Abu-Dief AM, Mostafa A, Hamdan SK. Ni(II) and Cu(II) complexes with ONNO asymetric tetradentate Schiff base ligand: synthesis, spectroscopic characterization, theoretical calculations, DNA interaction and antimicrobial studies, Applied Organometallic Chemistry, 31(e3555), 2017.
doi: 10.1002/aoc.3555

[16] Furche F, Rappoport D. Density functional methods for excited States: Equilibrium structure and electronic spectra, in M. Olivucci, editor, Computational photochemistry, volume 16 of
Theoretical and Computational Chemistry, chapter III, Elsevier, Amsterdam, 2005. ISBN: 9780080455198.

[17] Zhuang H, et al. Robust Photocatalytic H2O2 Production by Octahedral Cd3(C3N3S3)2 Coordination Polymer under Visible Light, Scientific Reports, 5: 16947, 2015.
doi: 10.1038/srep16947

[18] Kopel P, et al. Biological Activity and Molecular Structures of Bis(benzimidazole) and Trithiocyanurate Complexes, Molecules, 20(6): 10360-76, 2015.
doi: 10.3390/molecules200610360

[19] He XX, Guo YM. Two Zn(II) coordination complexes assembled by trithiocyanuric acid and two different N-donor auxiliary ligands, Acta Crystallographica C Structural Chemistry, 70(8): 764-
769, 2014.
doi: 10.1107/S2053229614014260

[20] Čermáková Š, Herchel R, Trávníček Z, Šebela M. Syntheses and magnetic properties of trinuclear trithiocyanurato-bridged manganese(II) complexes involving bidentate aromatic N-donor
heterocycles. Inorganic Chemistry Communications, 13(6): 778-781, 2010.
doi: 10.1016/j.inoche.2010.03.045

[21] Jing C, Ji-Min X, Chang-Kun X, Yu Z, Jia C. Synthesis, Characterization and Photoluminescent Property of a Hexanuclear Nickel(II) Complex with Trithiocyanuric Acid, Chinese Journal
Inorganic Chemistry, 29(11): 2433-2437, 2013.
doi: 10.3969/J.ISSN.1001-4861.2013.00.339

[22] Abdel-Rahman LH, Ismail NM, Ismael M, Abu-Dief AM, Ahmed EAH. Synthesis, characterization, DFT calculations and biological studies of Mn(II), Fe(II), Co(II) and Cd(II) complexes based on a tetradentate ONNO donor Schiff base ligand. Journal of Molecular Structure, 1134: 851-862, 2017.
doi: 10.1016/j.molstruc.2017.01.036

[23] Saleh Z, Askar F, Ridha S. Synthesis, Characterization and DFT Calculations of 1,4-diphenyl-3-(p-nitrophenylamino)-1,2,4-triazolium Hydroxide Inner Salt (Nitronitron) by 1H NMR,
FT-IR, UV/Vis and HOMO-LUMO Analysis, International Journal of Material Chemistry, 5(2): 31-43, 2015.
doi: 10.5923/j.ijmc.20150502.02

[24] Ridha S, Saleh Z, Askar F. Theoretical and Experimental Study for FT-IR and UV/VIS Spectra of 1,4-diphenyl-3-(phenylammonio)-1H-1,2,4-triazolium(inner salt) by Using DFT Approach, Physical
Chemistry, 5(1): 6-15, 2015.
doi: 10.5923/j.pc.20150501.02

[25] Osowole AA, Ekennia AC, Olubiyi OO, Olagunju M. Synthesis, Spectral, Thermal, Antibacterial and Molecular docking Studies of Some Metal(II) Complexes of 2-(1,3-benzothiazol-2-ylamino) naphthalene-1,4-dione, Research on Chemical Intermediates, 43(4): 2565-2585, 2.017.
doi: 10.1007/s11164-016-2780-8

[26] Biswal HS. Hydrogen Bonds Involving Sulfur: New Insights from ab Initio Calculations and Gas Phase Laser Spectroscopy. Noncovalent Forces, Cham: Springer International Publishing, pp.15-45. 2015.
doi: 10.1007/978-3-319-14163-3_2

[27] Junyao Y, Huanyan X. Degradation of Organic Dyes over Polymeric Photocatalyst C3N3S3, International Conference on Mechatronics, Electronic, Industrial and Control Enginbeering (MEICE 2014), pp. 349-352, 2014.
doi: 10.2991/meic-14.2014.78

[28] Henke K, Hutchison AR, Krepps M, Parkin S, Atwood DA. Chemistry of 2,4,6-Trimercapto-1,3,5-triazine (TMT): Acid Dissociation Constants and Group 2 Complexes, Inorganic Chemistry, 40: 4443-4447, 2001.
doi: 10.1021/IC0103188

[29] Chudy JC, Dalziel JAW. Metal complexes of 1,3,5-triazine-2,4,6-trithiol. Journal of Inorganic and Nuclear Chemistry, 37(12): 2459-2461, 1975.
doi: 10.1016/0022-1902(75)80870-0

[30] Kopel P, Doležal K, Machala L, Langer V. Synthesis, characterization and screening of biological activity of Zn(II), Fe(II) and Mn(II) complexes with trithiocyanuric acid, Polyhedron, 26(8): 1583-1589, 2007.
doi: 10.1016/j.poly.2006.11.022

[31] Salzner U. Quantitatively Correct UV-vis Spectrum of Ferrocene with TDB3LYP, Journal of Chemical Theory and Computation, 9(9): 4064-4073, 2013.
doi: 10.1021/ct400322v

[32] Ronca E, De Angelis F, Fantacci S. Time-Dependent Density Functional Theory Modeling of Spin-Orbit Coupling in Rutheniyum and Osmnium Solar Cell Sensitizers, Journal of Physical Chemistry C, 118(30): 17067-17078, 2014.
doi: 10.1021/jp500869r

[33] Ekennia, AC, Osowole AA, Olasunkanmi LO, Onwudiwe DC, Olubiyi OO, Ebenso EE. Synthesis, characterization, DFT calculations and molecular dicking studies of meta (II) complex,
Journal of Molecular Structure, 1150: 279-202, 2017.
doi: 10.1016/j.molstruc.2017.08.085

[34] Gökşen US, Alpaslan YB, Kelekçi NG, Işık Ş, Ekizoğlu M. Synthesis, crystal structures and theoretical calculations of new 1-[2-(5-chloro-2-benzoxazolinone-3-yl)acetyl]-3,5-diphenyl-4,5-
dihydro-(1H)-pyrazoles. Journal of Molecular Structure, 1039: 71-83, 2013.
doi: 10.1016/j.molstruc.2013.01.066
How to Cite
Jaramillo-Fierro, X. V., Zambrano, C., Fernández, F., Saenz-Puche, R., Costa, C., Guerrero, V., & González, S. (2018). Synthesis, characterization and theoretical calculations of Cu(I) complex of trithiocyanuric acid [Cu(ttc)3]. Universitas Scientiarum, 23(2), 241–266.
Química Analítica / Analytic Chemistry / Química Analítica