Abstract
The vibrational spectra of calixarenes with azobenzene units having sulfonate (p-SAC) and carboxylate (p-CAC) groups in the para position were recorded and analyzed. The optimization of the structure and analysis of normal vibration for calixarenes were performed using the DFT method. The calculated geometric parameters, the frequencies of the harmonic oscillations, the band intensities in the IR spectra, and the Raman scattering activity of the calixarenes are consistent with the experimental data. The p-CAC and p-SAC calix[4]arene molecules are in conical conformation due to the ring system of H-bonds along the low rim. The H-bond is weaker in the p-SAC molecule. The orientation of the aromatic moieties depends on the type of terminal functional groups. The energy differences between the E- and Z-forms of azobenzene groups in p-CAC and p-SAC are 60.8 and 62.6 kcal/mol, respectively. The experimental vibrational spectra of the calixarenes were interpreted using the potential energy distribution. Bands characteristic of trans and cis conformations of azobenzene fragments have been assigned. The HOMO and LUMO frontal molecular orbitals of the calixarene molecules are localized. The studied calixarenes can be used as antioxidants for thermal and light stabilization of polymer building materials.
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References
Gutsche, C.D.: Calixarene. An Introduction. The Royal Society of Chemistry, Cambridge (2008)
Ovsyannikov, A.S., Solovieva, S.E., Antipin, I.S., Ferlay, S.: Coordination polymers based on calixarene derivatives: structures and properties. Coord. Chem. Rev. 352, 151–186 (2017). https://doi.org/10.1016/j.ccr.2017.09.004
Vicens, J., Harrowfield, J., Baklouti, L. (eds.): Calixarenes in the Nanoworld. Springer, Heidelberg (2007). https://doi.org/10.1007/978-1-4020-5022-4
Solovieva, S.E., Burilov, V.A., Antipin, I.S.: Thiacalix[4]arene’s lower rim derivatives: synthesis and supramolecular properties. Macroheterocycles 10(1), 134–136 (2017). https://doi.org/10.6060/mhc170512a
Perret, F., Coleman, A.W.: Biochemistry of anionic calix[n]arenes. Chem. Commun. 47(26), 7303–7319 (2011). https://doi.org/10.1039/c1cc11541c
Kashapov, R.R., et al.: Self-aggregation and solubilizing properties of the supramolecular system based on azobenzenesulfonate calix[4]arene and CTAB. Macroheterocycles 10(4–5), 454–459 (2017). https://doi.org/10.6060/mhc171146k
Bonvallet, P.A., Mullen, M.R., Evans, P.J., Stoltz, K.L., Story, E.N.: Improved functionality and control in the isomerisation of a calix[4]arene-capped azobenzene. Tetr. Lett. 52(10), 1117–1120 (2011). https://doi.org/10.1016/j.tetlet.2010.12.107
Banadara, H.M.D., Burdette, S.C.: Photoisomerization in different classes of azobenzene. Chem. Soc. Rev. 41(5), 1809–1825 (2012). https://doi.org/10.1039/c1cs15179g
Furer, V.L., Potapova, L.I., Kovalenko, V.I.: DFT study of hydrogen bonding and IR spectra of calix[6]arene. J. Mol. Struct. 1128, 439–447 (2017). https://doi.org/10.1016/j.molstruc.2016.09.010
Furer, V.L., Vandyukov, A.E., Zaripov, S.R., Solovieva, S.E., Antipin, I.S., Kovalenko, V.I.: FT-IR and FT-Raman study of hydrogen bonding in p-alkylcalix[8]arenes. Vibr. Spec. 95(1), 38–43 (2018). https://doi.org/10.1016/j.vibspec.2018.01.006
Becke, A.D.: Density-functional thermochemistry. III. The role of exact exchange. J. Chem. Phys. 98(7), 5648–5652 (1993). https://doi.org/10.1063/1.464913
Lee, C., Yang, W., Parr, R.G.: Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phys. Rev. B 37(2), 785–789 (1988). https://doi.org/10.1103/PhysRevB.37.785
Frisch, M.J.: Gaussian 09 Revision C.01. Gaussian Inc., Wallingford (2010)
Ehlinger, N., Perrin, M.: Structure of p-tetrakis-(4-nitrophenylazo)calix[4]-arene-4-picoline (1:4) complex. J. Incl. Phenom. 22(1), 33–40 (1955). https://doi.org/10.1007/BF00706496
Sipachev, V.A.: Calculation of shrinkage corrections in harmonic approximation. J. Mol. Struct. (THEOCHEM) 121(1), 143–151 (1985). https://doi.org/10.1016/0166-1280(85)80054-3
Parr, R.G., Pearson, R.G.: Absolute hardness: companion parameter to absolute electronegativity. J. Am. Chem. Soc. 105(26), 7512–7516 (1983). https://doi.org/10.1021/ja00364a005
Glendening, E.D., Landis, C.R., Weinhold, F.: Natural bond orbital methods. Comput. Mol. Sci. 2(1), 1–42 (2012). https://doi.org/10.1002/wcms.51
Atwood, J.L., Orr, G.W., Hamada, F., Vincent, R.L., Bott, S.G., Robinson, K.D.: Calixarenes as second-sphere ligands for transition metal ions. Synthesis and crystal structure of [(H2O)5Ni(NC5H5)]2(Na)[calix[4]arene sulfonate]∙3.5 H2O and [(H2O)4Cu(NC5H5)2]-(H3O3)3 [calix[4]arene sulfonate] ∙ 10 H2O. J. Incl. Phenom. 14(1), 37–46 (1992)
Ugozzoli, F., Andretti, G.D.: Symbolic representation of the molecular conformation of calixarenes. J. Incl. Phenom. 13(4), 337–348 (1992). https://doi.org/10.1007/BF01133233
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Furer, V., Vandyukov, A., Popova, E., Solovieva, S., Antipin, I. (2021). Vibrational Spectra of p-Carboxylate and p-Sulfonate Azocalix[4]arene. In: Vatin, N. (eds) Proceedings of STCCE 2021. STCCE 2021. Lecture Notes in Civil Engineering, vol 169. Springer, Cham. https://doi.org/10.1007/978-3-030-80103-8_3
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