A semi-empirical estimation of ground and excited state dipole moments of zinc phthalocyanine from solvatochromic shift data

  • Abstract
  • Keywords
  • References
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  • Abstract

    A semi-empirical determination of ground and excited state dipole moments of zinc phthalocyanine (ZnPc) from solvatochromic shifts is hereby presented. The ratio of the excited- and ground-state dipole moments of ZnPc ( ) was estimated by a combination of the Bakshiev and the Kawski-Chamma-Viallet’s equations, while the difference in the excited- and ground-state dipole moments (Dm) was estimated usingthe molecular-microscopic solvent polarity parameters ( ), alongside the Stokes’ shifts (Dῡ) in the various solvents. The dipole moment of ZnPc is significantly higher in the excited singlet state (me = 3.12 D) than in the ground state (mg = 1.50 D). Obviously charge separation is greater in the excited state of ZnPc than in its ground state.



  • Keywords

    Dipole Moment; Excited State; Ground State; Solvatochromism; Zinc Phthalocyanine.

  • References

      [1] Aaron JJ, Tine A, Gaye MD, Parkanyi C, Boniface C &Bieze TWN (1991) Effects of solvent on the electronic absorption and fluorescence spectra of quinazolines, and determination of their ground and excited singlet-state dipole moments. Spectrochimica Acta Part A: Molecular Spectroscopy 47A, 419-430.https://doi.org/10.1016/0584-8539(91)80119-4.

      [2] Bakshiev NG (1964) Universal intermolecular interactions and their effect on the position of the electronic spectra of molecules in two component solutions. Optics and Spectroscopy 16, 821–832.

      [3] Baumann W (1989) Physical Methods of Chemistry (Rossiter BW & Hamilton JF eds.), John Wiley and Sons, New Jersey, Vol. 38, p. 45.

      [4] Campidelli S, Ballesteros B. Filoramo A, Diaz D, De la Torre G, Torres T, Rahman GMA, Aminur EC, Kiessling D, Werner F, Sgobba V, Guldi DM, Cioffi C, Prato M &Bourgoin J-P (2008) Facile Decoration of Functionalized Single-Wall Carbon Nanotubes with Phthalocyanines via “Click Chemistry. Journal of American Chemical Society 130, 11503-11509.https://doi.org/10.1021/ja8033262.

      [5] Chamma A &Viallet P (1970) De´termination du moment dipolaired’une molecule dansUNe´tat excite singulet L application a´ l’indole, au benzimidazoleET a´ l’indazole. ComptesRendus de l Académie des Sciences - Series C – Chemistry 270, 1901–1904.

      [6] Chandrasekhar K, Naik LR, Suresh HM & Math NN (2006) Steady-state absorption and fluorescence study: Dipole moments of coumarins. Indian Journal of Pure and Applied Physics 44, 292-299.

      [7] Cid J-J, Yum J-H, Jang S-R, Nazeeruddin MK, Martinez-Ferrero E, Palomares E, Ko J, Graetzel M & Torres T (2007) Molecular Cosensitization for Efficient Panchromatic Dye‐Sensitized Solar Cells. Angewandte Chemie International Edition 46, 8358-8362.https://doi.org/10.1002/anie.200703106.

      [8] Czekalla J (1960) Elektrischefluoreszenzpolarisation: die bestimmung von dipolmomentenangeregtermoleküleausdemfolarisationsgrad der fluoreszenz in starkenelektrischenfeldern. ZeitschriftfürElektrochemie 64, 1221-1228.

      [9] De la Torre G, Vazquez P & Torres T (2004) Role of structural factors in the nonlinear optical properties of phthalocyanines and related compounds. Chemical Reviews 104, 3723-3750.https://doi.org/10.1021/cr030206t.

      [10] Gao W & Kahn a (2002) Electronic structure and current injection in zinc phthalocyanine doped with tetrafluorotetracyanoquinodimethane: Interface versus bulk effects. Organic Electronics 3, 53–63.https://doi.org/10.1016/S1566-1199(02)00033-2.

      [11] Higasi K (1953) the Dipole Moments of Fluorenone Peroxide and Bishydroperoxide. Bulletin of the Chemical Society of Japan 39, 248-250.https://doi.org/10.1246/bcsj.26.248.

      [12] Husain MM, Sindhu R &Tandon HC (2012) Photophysical properties and estimation of ground and excited state dipole moments of 7‐diethylamino and 7‐diethylamino‐4‐methyl coumarin dyes from absorption and emission spectra. European Journal of Chemistry 3, 87‐93.https://doi.org/10.5155/eurjchem.3.1.87-93.519.

      [13] Isago H, Kagaya Y & Matsushita a (2004) Solvatochromic Shift of Phthalocyanine Q-band Governed by a Single Solvent Parameter. Chemistry Letters 33, 862-863.https://doi.org/10.1246/cl.2004.862.

      [14] Kabatc J, Osmialowski&Paczkowski J (2006) the Experimental Studies on the Determination of the Ground and Excited State Dipole Moments of Some Hemicyanine Dyes. SpectrochimicaActa Part A 63, 524-531.https://doi.org/10.1016/j.saa.2005.05.039.

      [15] Kadish KM, Smith KM & and Guilard R (2003) the Porphyrin Handbook, Volumes 15-20. Academic Press, San Diego CA.

      [16] Kawski A (1966) Der wellenzahl von elektronenbandenlumineszie—rendenmolekille. ActaPhysicaPolonica 29, 507–518.

      [17] Kobayashi T, Ashida, T, Uyeda N, Surro E &Kakuda M (1971) The crystal structure of the 2:3 complex of zinc phthalocyanine and n-hexylamine. Bulletin of the Chemical Society of Japan 44, 2095-2103.https://doi.org/10.1246/bcsj.44.2095.

      [18] Liptay W (1974) Excited States (Lim EC ed.), Academic Press, INC New York, Vol. 1, pp. 129-229.

      [19] Mack J. &Stillman MJ (1994) Photochemical formation of the anion radical of zinc phthalocyanine and analysis of the absorption and magnetic circular dichroism spectral data - Assignment of the optical spectrum of [ZnPc(-3)]-. Journal of American Chemical Society 116, 1292-1304.https://doi.org/10.1021/ja00083a015.

      [20] Nadaf YF, Mulimani BG, Gopal M &Inamdar SR (2004) Ground and excited state dipole moments of some exalite UV laser dyes from solvatochromic method using solvent polarity parameters. Journal of Molecular Structure (Theochem) 678, 177–181.https://doi.org/10.1016/j.theochem.2004.01.049.

      [21] Ogunsipe A, Maree D &Nyokong T (2004) Solvent effects on the photochemical and fluorescence properties of zinc phthalocyanine derivatives. Journal of Molecular Structure 650, 131-140. https://doi.org/10.1016/S0022-2860(03)00155-8.

      [22] Ogunsipea&Nyokong T (2005) Photophysical and photochemical studies of non-transition metal phthalocyaninesulphonates in aqueous and non-aqueous media. Journal of Photochemistry Photobiology A: Chemistry 173, 211-220. https://doi.org/10.1016/j.jphotochem.2005.03.001.

      [23] OgunsipeA&Nyokong T (2011) Solvent Effects on the photophysicochemical properties of tetra (tert-butylphenoxy)phthalocyaninatozinc (II). ActaPhysicochimicaSinica 27, 1045-1052.

      [24] Ogunsipe A (2018) Solvent effects on the spectral properties of Rhodamine 6G: Estimation of ground and excited state dipole moments. Journal of Solution Chemistry 47, 203–219.https://doi.org/10.1007/s10953-017-0706-8.

      [25] Pinzon JR, Plonska-Brzezinska ME, Cardona CM, Athans AJ, Gayathri SS, Guldi DM, Herranz MA, Martin N, Torres T &Echegoyen L (2008) Sc3N@C80-Ferrocene electron-donor/acceptor conjugates as promising materials for photovoltaic applications. Angewandte Chemie International Edition 47, 4173-4176.https://doi.org/10.1002/anie.200800473.

      [26] Ravi M, Samanta A &Radhakrishnan TP (1994) Excited state dipole moments from an efficient analysis of solvatochromic stokes shift data. Journal of Physical Chemistry 98, 9133–9136.https://doi.org/10.1021/j100088a007.

      [27] Reichardt C &Harbusch-Gornert E (1983) Überpyridinium‐N‐phenolat‐betaine und ihreverwendungzurcharakterisierung der polarität von lösungsmitteln, X. Erweiterung, korrektur und neudefinition der ET‐lösungsmittelpolaritätsskalamithilfeeineslipophilen penta‐tert‐butyl‐substituiertenpyridinium‐N‐phenolat‐betainfarbstoffes. Liebigs Annalen der Chemie 721–743.https://doi.org/10.1002/jlac.198319830502.

      [28] Reichardt C (1994) Solvatochromic dyes as solvent polarity indicators. Chemical Reviews 94, 2319–3458.https://doi.org/10.1021/cr00032a005.

      [29] Sakamoto K, Okumura E and Hirohashi R (2004) Phthalocyanine as functional dyes. IPC, Tokyo.

      [30] Tomoda H, Saito S &Shiraishi S (1983) Synthesis of metallophthalocyanines from phthalonitrile with strong organic bases. Chemistry Letters 313-316.https://doi.org/10.1246/cl.1983.313.




Article ID: 11019
DOI: 10.14419/ijac.v6i2.11019

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