Theoretical calculation of influence of halogen at-oms (F, Cl, Br, I) on arylazopyridine (Azpy) ruthenium complexes behaving as photo sensitizers by DFT method

  • Authors

    • N'guessan Kouakou Nobel Université Nangui Abrogoua
    • Ouattara Wawohinlin Patrice Université Nangui Abrogoua
    • Bamba Kafoumba Université Nangui Abrogoua, 02 B.P. 801 Abidjan 02, Côte d’Ivoire.
    • Ziao Nahossé Université Nangui Abrogoua
    2018-02-16
    https://doi.org/10.14419/ijac.v6i1.9026
  • Azopyridine, Halide Atoms, NBO, NLMO, Ru(II) Complexes.

  • Abstract

    Photosensivity prediction of several azopyridine ruthenium complexes by DFT and TDDFT methods was performed. g-RuX2 (Azpy) 2 and d-RuX2(Azpy)2 where X stands for F, Cl, Br and I were studied todetermine their activities when halide atoms shift. So, frontier orbital, NBO, NLMO and MLCT transitions as well as an excited lifetime of those complexes was determined. The main difference between them stems from both the electronegativity of the halide atoms and the structure of each complex. Hence, the rank of halide's electronegativity that is as followscp(F)>cp (Cl)>cp (Br)>cp (I) has been discovered to influence all the reactivity of the complexes regardless their structure. Herein, the comparison with the gap energy shows that the most reactive complexes are those with fluorine atom. Especially, d-RuF2(Azpy)2 was admitted to be the most active isomer. Moreover, NBO calculation discloses that the complex becomes less ionic when the electronegativity decreases from F to I atoms. Furthermore, the calculation of NLMO orbitals shows that the bonding Ru-X are very strong. However, this strength decreases also from F to I and the nature of the bonding move from ionic to metallic. Moreover, the bonding from Npy and N2 with Ru are known to be the same confirming the bidentate state of Azpy ligand. Regarding the electronic prediction, the eight complexes are surely assumed to display MLCT transitions that originate the photosensitivity. However, the complex that requires the least energy remains d-RuF2(Azpy)2. This result was also determined by analyzing the excited lifetime that is the ability for a complex to longer linger in the cationic state. At last, we found out that with iodine atoms, the azopyridine ruthenium complex cannot behave as photosensitize dye insofar as I atom hides the main orbitals from Ru regardless the symmetry.

  • References

    1. [1] Adamo C &Jacquemin D (2013) Chem. Soc. Rev, The calculations of excited-state properties with time-dependent density functional theory 42, 845-865. https://dx.doi.org/10.1039/c2cs.35394f

      [2] Affi ST, Bamba K &Ziao N (2015) Computational characterization of organometallic ligands coordinating metal: case of azopyridine ligands, JTCC 14 (1): 1550006. https://doi.org/10.1142/S0219633615500066.

      [3] Bamba K, Leger J-M, Ganier E, Bachmann C, Servat K &Kokoh KB * (2004) Selective electro-oxidation of D-glucose by Rucl2 (azpy) 2 complexes as electrochemical mediators. Electrochimicaacta 50, 3341- 3346. https://doi.org/10.1016/j.electacta.2004.12.007.

      [4] Bamba K, Ouattara WP, N’Guessan KN &Ziao N (2016) SARs Investigation of α-, β-, γ-, δ-, ε -RuCl2(Azpy)2 complexes as antitumor drugs. Computational Chemistry 4, 1-10. https://doi.org/10.4236/cc.2016.41001.

      [5] Boa T, Krause K & Krause R A (1988) Hydroxide-assisted stereospecific isomerization of a trans-dichlorobischelate of ruthenium (II), Inorg. Chem. 27, 759-761. https://doi.org/10.1021/ic00277a037.

      [6] Chaofan S, Yuanzuo Li, Peng S &Fengcai M (2016) An Experimental and Theoretical Investigation of the Electronic Structures and Photoelectrical Properties of Ethyl Red and Carminic Acid for DSSC Application, Materials vol. 9, p. 813. https://doi.org/10.3390/ma9100813.

      [7] Chen JC, Li JL, Qian L &Zheng KC, (2005) Electronic Structures and SARs of the Isomeric Complexes α-, β-, γ-[Ru(mazpy)2Cl2] with Different Antitumor Activities, Journal of Molecular Structure: THEOCHEM vol. 728, pp. 93-101. https://doi.org/10.1016/j.theochem.2005.05.005.

      [8] Frisch M J, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Montgomery JA, VrevenJrT, Kudin KN, Burant JC, Millam JM, Iyengar SS, Tomasi J, Barone V, Mennucci B, Cossi M, Scalmani G, Rega N, Petersson GA, Nakatsuji H, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Klene M, Li X, Knox JE, Hratchian HP, Cross J B, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Ayala PY, Morokuma K, Voth GA, Salvador P, Dannenberg JJ, Zakrzewski VG, Dapprich S, Daniels AD, Strain MC, Farkas O, Malick DK, Rabuck AD, Raghavachari K, Foresman JB, Ortiz JV, Cui Q, Baboul AG, Clifford S, Cioslowski J, Stefanov BB, Liu G, Liashenko A, Piskorz P, Komaromi I, Martin RL, Fox DJ, Keith T, Al-Laham MA, Peng CY, Nanayakkara A, Challacombe M, Gill PMW, Johnson B, Chen W, Wong MW, Gonzalez C &Pople JA, Gaussian, Inc., Pittsburgh PA, 2003.

      [9] Gowami S, Chakravarty AR &Chakrovorty A (1981) Chemistry of ruthenium. 2. Synthesis, Structure, and Redox Properties of 2-(Arylazo) pyridine Complexes, Inorg. Chem., 20, 2246-2250. https://doi.org/10.1021/ic50221a061.

      [10] Jorna AJ, Boelrijk AEM, Hoorn HJ &Reedijk J (1996) Heterogenization of a Ruthenium Catalyst on Silica and Its Application in Alcohol Oxidation and StilbeneEpoxidation. Reactive & Functional Polymers 29, 101-114. https://doi.org/10.1016/1381-5148(96)00005-3.

      [11] Krause RA & Krause K (1980) Chemistry of bipyridyl like ligands. Isomeric complexes of ruthenium (II) with 2-(phenylazo) pyridine. Inorg. Chem. 19, 2600-2603. https://doi.org/10.1021/ic50211a024.

      [12] Krause RA & Krause K (1982) Chemistry of Bipyridyl-like ligands. 2. Mixed Complexes of ruthenium (II) with 2-phenylazopyridine: a new p-bending probe, inorg. Chem., 21, 1714-1720. https://doi.org/10.1021/ic00135a002.

      [13] Misra TK, Das D &Sinha C (1997) Chemistry of azoimidazoles: synthesis, spectral characterization and redox properties of bis(N (1)-alkyl-2-(arylazo)imidazole) copper (I) and silver(I) complexes. Polyhedron 16, 23, 4163-4170. https://doi.org/10.1016/S0277-5387(97)00127-7.

      [14] Nobel NK, Bamba K, Patrice OW &Ziao N (2017) NBO population analysis and electronic calculation of four azopyridine ruthenium complexes by DFT method. Computational Chemistry, 5, 51-64. http://dx.doi.org/10.4236/cc2017.51005

      [15] Reed AE, Curtiss LA &Weinhold F, (1988) Intermolecular interactions from a natural bond orbital, donor-acceptor viewpoint, Chem. Rev. 88, 899-926. https://doi.org/10.1021/cr00088a005.

      [16] Reedijk J &Bouwman E (1999), bioinorganic catalysis (Dekker, New-york). https://doi.org/10.1201/9780203908457.

      [17] Reedijk J (2003) new clues for platinum antitumor chemistry: kinetically controlled metal binding to DNA, PNAS 100(7), and 3611-3616. https://doi.org/10.1073/pnas.0737293100.

      [18] Shriver DF & Atkins PW (1999) inorganic chemistry, 3rd edition, Oxford University Press, 406.

      [19] Velders AH, Van der Schilden K, Hoste ACG, Reedijk J, Kooijman H & Speck A L (2004) Dichlorobis(2-phenylazopyridine)ruthenium(II) complexes: characterization, spectroscopic and structure properies of four isomers. Dalton Trans., 448-455. https://doi.org/10.1039/B313182C.

      [20] Weinhold F & Landis CR (2001) Chem. Educ. Res. Pract. Eur., Natural Bond Orbitals and extensions of Localized bonding concepts, chemistry education Research and Practice 2, 91-104.

  • Downloads

  • How to Cite

    Kouakou Nobel, N., Wawohinlin Patrice, O., Kafoumba, B., & Nahossé, Z. (2018). Theoretical calculation of influence of halogen at-oms (F, Cl, Br, I) on arylazopyridine (Azpy) ruthenium complexes behaving as photo sensitizers by DFT method. International Journal of Advanced Chemistry, 6(1), 67-73. https://doi.org/10.14419/ijac.v6i1.9026

    Received date: 2018-01-04

    Accepted date: 2018-02-05

    Published date: 2018-02-16