Conjugated prototropic and ring opening rearrangements in Schiff base derivatives of formyl functionalized 2-oxaindane series spiropyran: synthesis, NMR, IR, UV/Vis, and DFT study
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Condensation reaction products of formyl derivative of the 2-oxaindane series spiropyran (7-hydroxy-3′,3′-dimethyl-3’H-spiro [chromene-2,1′-isobenzofuran]-8-carbaldehyde) with several 2-amino-4-R-phenols (R = H, tBu, Сl, NO2) were synthesized and studied with the help of IR, UV/Vis, and NMR spectroscopy. It was shown that in contrast with mother spiropyran existing in closed spiro-form, all the compounds in the solution (DMSO, acetonitrile) and in solid state exist in thermodynamically stable merocyanine keto-enamine tautomeric form due to migration of the proton of 7-hydroxy group to azomethine nitrogen, conjugated with electrocyclic opening of the spirounit in the non-stable Schiff bases. In DMSO solution of merocyanine keto-enamines (R = H, tBu, Сl), dynamic equilibrium of Z,E-isomers in respect to C=C-N exocyclic double bond is observed (of which Z-one is the major component); in case of R = NO2, two additional isomers are registered. Upon protonation, strong absorption bands with maxima at the 580–590-nm spectral region are developed, while second protonation leads to hypsochromic shift of the longest wavelength absorption band to ca. 480 nm. Experimental results are supported with the DFT quantum chemical modeling of possible isomers of the obtained substances and their spectral properties (B3LYP/6-311++G(d,p) level of theory for geometry optimizations and spectra modeling).
KeywordsSpiropyrans DFT calculations Merocyanine Acidochromism
Spectral data were obtained on the equipment of Joint Resource Centre “Molecular Spectroscopy.” DFT calculations were performed at JRC “High-performance calculations” of Southern Federal University.
Compliance with ethical standards
The authors declare that they have no competing interests.
- 1.Organic Photochromes AV (1990) Eltsov. Consultants Bureau, New York, p 280Google Scholar
- 3.Photochromism (2003) In: Durr H, Bouas-Laurent H (eds) Molecules and systems: molecules and systems. Elsevier, Amsterdam, p 1218Google Scholar
- 21.Kume S, Nishihara H (2007) Metal-based photoswitches derived from photoisomerization. In: Yam VWW (ed) Photofunctional transition metal complexes. Springer, Berlin, pp 79–112Google Scholar
- 26.M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, V.B. G. Scalmani, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, , O.K. Y. Honda, H. Nakai, T. Vreven, J. A. Montgomery, Jr, J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, O. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, D. J. Fox, Gaussian 09, revision A.02 Gaussian, Inc., Wallingford, 2009Google Scholar
- 33.Casida ME, Jamorski C, Casida KC, Salahub DR (1998) Molecular excitation energies to high-lying bound states from time-dependent density-functional response theory: characterization and correction of the time-dependent local density approximation ionization threshold. J Chem Phys 108:4439–4449CrossRefGoogle Scholar