The role of the molecular structure in the formation of the bathochromic shift of the S0 → S1 transition for a family of N-substituted porphine derivatives was studied. Molecular conformations of porphine, four of its N-substituted derivatives, and two model porphines with selected fixed bond angles and lengths in the macrocycles were optimized, the energies of the molecular orbitals were determined, and electronic absorption spectra were calculated using quantum-chemistry methods. It was found that N-substitution led to significant pyramidalization of the nitrogen atom. The degree of hybridization λ2 of the N atom depended on the volume of the N-substituent and reached a value of λ2 = 2.729 in porphyrin H(N–CCl3)P. The degree of hybridization λ2 of the N atom was established as the factor determining the energy of the long-wavelength S0 → S1 transition because the conjugation along the inner Ca–N–Ca fragment of the pyrrole ring decreased upon pyramidalization of the N atom while π-conjugation via the outer Ca–Cb–Cb–Ca fragment, which led to an increase in the size of the conjugated π-system, simultaneously strengthened. The tilt of the N-substituted pyrrole ring relative to the macrocycle mean plane and the electron-donating/electron-withdrawing properties of the N-substituents did not directly affect the bathochromic shift of the S0 → S1 transition.
Similar content being viewed by others
References
J. A. Shelnutt, X.-Z. Song, J.-G. Ma, S.-L. Jia, W. Jentzen, and C. J. Medforth, Chem. Soc. Rev., 27, 31–41 (1998).
B. Roder, M. Buchner, I. Ruckmann, and M. O. Senge, Photochem. Photobiol. Sci., 9, 1152–1158 (2010).
K. M. Barkigia, L. Chantrapunong, K. M. Smith, and J. Fajer, J. Am. Chem. Soc., 110, 7566–7567 (1988).
L. D. Sparks, C. J. Medforth, M.-S. Park, J. R. Chamberlain, M. R. Ondrias, M. O. Senge, K. M. Smith, and J. A. Shelnutt, J. Am. Chem. Soc., 115, 581–592 (1993).
C. J. Medforth, M. O. Senge, K. M. Smith, L. D. Sparks, and J. A. Shelnutt, J. Am. Chem. Soc., 114, 9859–9869 (1992).
S. G. DiMagno, A. K. Wertsching, and C. R. Ross, II, J. Am. Chem. Soc., 117, 8279–8280 (1995).
A. B. J. Parusel, T. Wondimagegn, and A. Ghosh, J. Am. Chem. Soc., 122, 6371–6374 (2000).
A. K. Wertsching, A. S. Koch, and S. G. DiMagno, J. Am. Chem. Soc., 123, 3932–3939 (2001).
H. Ryeng and A. Ghosh, J. Am. Chem. Soc., 124, 8099–8103 (2002).
R. E. Haddard, S. Gazeau, J. Pecaut, J.-C. Marchon, C. J. Medforth, and J. A. Shelnutt, J. Am. Chem. Soc., 125, 1253–1268 (2003).
V. I. Gael’, V. A. Kuz’mitskii, and K. N. Solov’ev, J. Appl. Spectrosc., 66, 627–631 (1999).
V. I. Gael’, V. A. Kuz’mitskii, and K. N. Solov’ev, J. Appl. Spectrosc., 67, 956–965 (2000).
M. O. Senge, in: The Porphyrin Handbook, K. M. Kadish, K. M. Smith, and R. Guillard (Eds.), Vol. 1, New York (2000), pp. 239–347.
D. K. Lavallee, The Chemistry and Biochemistry of N-Substituted Porphyrins, VCH Publishers, New York (1987).
N. N. Kruk, L. L. Gladkov, D. V. Klenitskii, and A. B. Krylov, Tr. BGTU, Ser. 3: Fiz.-Mat. Nauki Inf., 266, 34–41 (2023).
D. N. Laikov, Chem. Phys. Lett., 281, 151–156 (1997).
D. N. Laikov and Yu. A. Ustynyuk, Russ. Chem. Bull., 54, 820–826 (2005).
M. O. Senge, S. A. MacGowan, and J. O'Brien, Chem. Commun. (Cambridge, U. K.), 51, 17031–17063 (2015).
T. M. Krygowski, J. Chem. Inf. Comp. Sci., 33, 70–78 (1993).
I. V. Alabugin, S. Bresch, and G. P. Gomes, J. Phys. Org. Chem., 28, 147–162 (2015).
N. N. Kruk, Structure and Optical Properties of Tetrapyrrole Compounds [in Russian], BGTU, Minsk (2019).
O. V. Sverdlova, Electronic Spectra in Organic Chemistry [in Russian], Khimiya, Leningrad (1973).
S. L. Murov, I. Carmichael, and G. L. Hug, Handbook of Photochemistry, 2nd edn., New York (1993).
K. Hansch, A. Leo, and R. W. Taft, Chem. Rev., 91, 165–195 (1991).
A. I. Volkov, Structure of Atoms and the Periodic Law [in Russian], OOO Novoe Znanie, Moscow (2006).
M. Gouterman, in: The Porphyrins, D. Dolphin (Ed.), Vol. 3, New York (1978).
M. Roucan, M. Keilmann, S. J. Connon, S. S. R. Bernhard, and M. O. Senge, Chem. Commun., 54, 26–29 (2018).
Author information
Authors and Affiliations
Corresponding author
Additional information
Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 90, No. 4, pp. 561–568, July–August, 2023.
Rights and permissions
Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.
About this article
Cite this article
Gladkov, L.L., Klenitsky, D.V. & Kruk, M.M. Mechanisms of Bathochromic Band Shifts in Absorption Spectra of N-Substituted Porphine Derivatives. J Appl Spectrosc 90, 754–760 (2023). https://doi.org/10.1007/s10812-023-01592-w
Received:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10812-023-01592-w