Spectral-Luminescent Properties of meso-Tetraarylporphyrins Revisited: The Role of Aryl Type, Substitution Pattern and Macrocycle Core Protonation

Irina V. Vershilovskaya,^a Stefano Stefani,^b Pieter Verstappen,^c Thien H. Ngo,^b,d@¹ Ivan G. Scheblykin,^e Wim Dehaen,^f Wouter Maes,^c@2 and Mikalai M. Kruk^a@³

^aBelarussian State Technological University, Physics Department, 220006 Minsk, Belarus

^bInstitut für Chemie und Biochemie, Freie Universität Berlin, 14195 Berlin, Germany

^cDesign & Synthesis of Organic Semiconductors (DSOS), Institute for Materials Research (IMO-IMOMEC), Hasselt University, B-3590 Diepenbeek, Belgium

^dInternational Center for Materials Nanoarchitectonics (MANA), National Institute for Materials Science (NIMS), 305-0044 Tsukuba, Ibaraki, Japan

^eLund University, Division of Chemical Physics, 22100 Lund, Sweden

^fMolecular Design and Synthesis, Department of Chemistry, KU Leuven, B-3001 Leuven, Belgium

^@1Corresponding author E-mail: krukmikalai@yahoo.com; m.kruk@belstu.by

^@2Corresponding author E-mail: wouter.maes@uhasselt.be

^@3Corresponding author E-mail: ngo.huynhthien@nims.go.jp

DOI: 10.6060/mhc160962n

Macroheterocycles 2017 10(3) 257-267

Both the ground (S₀) and the lowest singlet excited states (S₁) for a series of 5,10,15,20-tetraarylporphyrins consisting of two symmetrically and four asymmetrically substituted derivatives (A₄, AB₃, trans-A₂B₂, cis-A₂B₂, A₃B and B₄, where A=phenyl and B=mesityl) are studied by absorption and fluorescence spectroscopies. The rotational degree of freedom of the aryl rings is found to play a crucial role in the discrimination between the radiative and radiationless decays of the S₁states. This feature is dramatically enhanced upon going from the free base molecules to their mono- and diprotonated forms because of the nonplanar macrocycle conformation of the latters. The progressive A to B replacement of the aryl substituents leads to additive spectral changes over the whole series in the free base form. For both mono- and diprotonated species such a gradual additive pattern is broken by a “spectral jump” from the trans to the cis derivative, which is proposed to be a signature of the transition between two macrocycle conformations with different flexibility.

References:

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1. Smith K.M. In: The Porphyrin Handbook Vol. 1 (Kadish K.M., Smith K.M., Guillard R., Eds.) San Diego: World Scientific, 2000.

2. Milgrom L.R. The Colours of Life: An Introduction to the Chemistry of Porphyrins and Related Compounds. Oxford: Oxford University Press, 1997. 249 p.
https://doi.org/10.1002/adma.19970091516

3. Li L.L., Diau E.W.G. Chem. Soc. Rev. 2013, 42, 291–304.
https://doi.org/10.1039/C2CS35257E

4. Kesters J., Verstappen P., Kelchtermans M., Lutsen L., Vanderzande D., Maes W. Adv. Energy Mater. 2015, 1500218.
https://doi.org/10.1002/aenm.201500218

5. Bonnett R. Chemical Aspects of Photodynamic Therapy. Amsterdam: Gordon and Breach Science Publishers, 2000. 305 p.

6. Hecht S., Fréchet J.M.J. Angew. Chem. Int. Ed. 2001, 40, 75–91.
https://doi.org/10.1002/1521-3773(20010105)40:1<74::AID-ANIE74>3.0.CO;2-C

7. Lindsey J.S. meso-Tetraarylporphyrin Derivatives: New Synthetic Methodologies. In: The Porphyrin Handbook, vol. 2 (Kadish K.M., Smith K.M., Guillard R., Eds.) San Diego: World Scientific, 2000. p. 45–118.

8. Adler A.D., Longo F.R., Finarelli J.D., Goldmacher J., Assour J., Korsakoff L. J. Org. Chem. 1967, 325, 476.
https://doi.org/10.1021/jo01288a053

9. Shanmugathasan S., Edwards C., Boyle R.W. Tetrahedron 2000, 56, 1025–1046.
https://doi.org/10.1016/S0040-4020(99)00907-2

10. Stone A., Fleischer E.B. J. Am. Chem. Soc. 1968, 90, 2735–2748.
https://doi.org/10.1021/ja01013a001

11. Kobuke Y., Miyagi H. J. Am. Chem. Soc. 1994, 116, 4111–4112.
https://doi.org/10.1021/ja00088a070

12. Bruix M., Elguero J., Meutermans W. J. Chem. Res. (S) 1992, 370–371.

13. Furuta H., Maeda H., Furuta T., Osuka A. Org. Lett. 2000, 2, 187–189.
https://doi.org/10.1021/ol9912783

14. Gupta I., Hung C.-H., Ravikanth M. Eur. J. Org. Chem. 2003, 4392–4400.
https://doi.org/10.1002/ejoc.200300228

15. Bruekner C., Foss P.C.D., Sullivan J.O., Pelto R., Zeller M., Birge R.R., Crundwell G. Phys. Chem. Chem. Phys. 2006, 8, 2402–2412.
https://doi.org/10.1039/B600010J

16. Lee W.A., Gratzel M., Kalynasundaram K. Chem. Phys. Lett. 1984, 107, 308–313.
https://doi.org/10.1016/0009-2614(84)85135-0

17. Hambright P., Gore T., Burton M. Inorg. Chem. 1976, 15, 2314–2315.
https://doi.org/10.1021/ic50163a072

18. Thomas D.W., Martell A.E. J. Am. Chem. Soc. 1956, 78, 1335–1338.
https://doi.org/10.1021/ja01588a020

19. Meot-Ner M., Adler A.D. J. Am. Chem. Soc. 1975, 97, 5107–5111.
https://doi.org/10.1021/ja00851a014

20. Freitag R.A., Whitten D.G. J. Phys. Chem. 1983, 87, 3918–3925.
https://doi.org/10.1021/j100243a026

21. Wolberg A. J. Mol. Struct. 1974, 21, 61–66.
https://doi.org/10.1016/0022-2860(74)80031-1

22. Eaton S.S., Eaton G.R. J. Am. Chem. Soc. 1975, 97, 3660–3666.
https://doi.org/10.1021/ja00846a016

23. Quimby D.J., Longo F.R. J. Am. Chem. Soc. 1975, 97, 5111–5117.
https://doi.org/10.1021/ja00851a015

24. Egorova G.D., Knyukshto V.N., Solovyov K.N., Tsvirko M.P. Optika i Spectroskopiya [Optics and Spectroscopy] 1980, 48, 1101–1107 (in Russian).

25. Kalyanasundaram K. Inorg. Chem. 1984, 23, 2453-2459.
https://doi.org/10.1021/ic00184a019

26. Sutter T.P.J., Rahimi R., Hambright P., Bommer J.C., Kumar M., Neta P. J. Chem. Soc. Faraday Trans. 1993, 89, 495–502.
https://doi.org/10.1039/ft9938900495

27. Fonda H.N., Gilbert J.V., Cormier R.A., Sprague J.R., Kamioka K., Connoly J.S. J. Phys. Chem. 1993, 97, 7024–7033.
https://doi.org/10.1021/j100129a017

28. Knyukshto V.N., Solovyov K.N., Mironov A.F., Egorova G.D., Efimov A.V. Optika i Spectroskopiya [Optics and Spectroscopy] 1998, 85, 592–600 (in Russian).

29. Knyukshto V., Zenkevich E., Sagun E., Shulga A., Bachilo S. Chem. Phys. Lett. 1998, 297, 97–108.
https://doi.org/10.1016/S0009-2614(98)01096-3

30. Knyukshto V.N., Solovyov K.N., Egorova G.D. Biospectroscopy 1998, 4, 121–133.
https://doi.org/10.1002/(SICI)1520-6343(1998)4:2<121::AID-BSPY5>3.0.CO;2-8

31. Senge M.O. J. Photochem. Photobiol. B: Biol. 1992, 16, 3–36.
https://doi.org/10.1016/1011-1344(92)85150-S

32. Cheng B., Munro O.Q., Marques H.M., Scheidt W.R. J. Am. Chem. Soc. 1997, 119, 10732–10742.
https://doi.org/10.1021/ja9716214

33. Shelnutt J.A., Song X.-Z., Ma J.-G., Jia S.-L., Jentzen W., Medforth C.J. Chem. Soc. Rev. 1998, 27, 31–41.
https://doi.org/10.1039/a827031z

34. Rosa A., Ricciardi G., Baerends E.J., Romeo A., Scolaro L.M. J. Phys. Chem. A 2003, 107, 11468–11482.
https://doi.org/10.1021/jp030999n

35. Rosa A., Riccardi G., Baerends E.J. J. Phys. Chem. A 2006, 110, 5180–5190.
https://doi.org/10.1021/jp060931i

36. Kruk M.M., Starukhin A.S., Maes W. Macroheterocycles 2011, 4, 69–79.
https://doi.org/10.6060/mhc2011.2.01

37. De Luca G., Romeo A., Scolaro L.M., Ricciardi G., Rosa A. Inorg. Chem. 2007, 46, 5979–5988.
https://doi.org/10.1021/ic0703373

38. Presselt M., Dehaen W., Maes W., Klamt A., Martinez T., Beenken W.J.D., Kruk M.M. Phys. Chem. Chem. Phys. 2015, 17, 14096–14106.
https://doi.org/10.1039/C5CP01808K

39. Karotki A., Drobizhev M., Kruk M., Spangler C.W., Nickel E., Mamardashvili N., Rebane A. J. Opt. Soc. Am. B 2003, 20, 321–332.
https://doi.org/10.1364/JOSAB.20.000321

40. Kruk M.M., Braslavsky S.E. Photochem. Photobiol. Sci. 2012, 11, 972–978.
https://doi.org/10.1039/c2pp05368c

41. Maes W., Ngo T.H., Rong G., Starukhin A.S., Kruk M.M., Dehaen W. Eur. J. Org. Chem. 2010, 4, 2576–2586.
https://doi.org/10.1002/ejoc.201000180

42. Nguyen N.T., Hofkens J., Scheblykin I.G., Kruk M.M., Dehaen W. Eur. J. Org. Chem. 2014, 8, 1766–1777.
https://doi.org/10.1002/ejoc.201301158

43. Nguyen N.T., Couti-o-Gonzalez E., Hofkens J., Scheblykin I.G., Dehaen W., Kruk M.M. Macroheterocycles 2014, 7, 240–248.
https://doi.org/10.6060/mhc140717k

44. Kruk M.M, Vershilovskaya I.V., Stefani S., Verstappen P., Ngo T.H., Scheblykin I.G., Dehaen W., Maes W. 9-th International Conference on Porphyrins and Phthalocyanines ICPP-9: Book of Abstracts, Nanjing, China, July 3-8, 2016, 422.

45. Kruk M.M, Vershilovskaya I.V., Ngo T.H., Scheblykin I.G., Dehaen W., Maes W. Trudy BGTU [Proceedings of Belarusian State Technological University (BSTU)]: Physics, mathematics and computer science. 2016, 186(4), 16–20 (in Russian).

46. Lindsey J.S., Wagner R.W. J. Org. Chem. 1989, 54, 828–836.
https://doi.org/10.1021/jo00265a021

47. Kruk M.M., Braslavsky S.E. J. Phys. Chem. A 2006, 110, 3414–3425.
https://doi.org/10.1021/jp056896h

48. Gouterman M., Wagniere G., Snyder L.R. J. Mol. Spectrosc. 1963, 11, 108–127.
https://doi.org/10.1016/0022-2852(63)90011-0

49. Gouterman M. Optical spectra and electronic structure of porphyrins and related rings. In The Porphyrins, vol. 3, (Dolphin D., Ed.) New York: Academic Press, 1978. p. 1–165.
https://doi.org/10.1016/B978-0-12-220103-5.50008-8

50. Starukhin A.S., Kruk M.M., Gladkova O.L., Maes W. Macroheterocycles 2011, 4, 85–88.
https://doi.org/10.6060/mhc2011.2.03

51. Kruk M.M., Ngo T.H., Verstappen P., Starukhin A.S., Hofkens J., Dehaen W., Maes W. J. Phys. Chem. A 2012, 116, 10695–10703.
https://doi.org/10.1021/jp305326x

52. Antonov L., Nedeltchava D. Chem. Soc. Rev. 2000, 29, 217–227.
https://doi.org/10.1039/a900007k

53. Kruk M.M., Starukhin A.S., Mamardashvili N.Z., Mamardashvili G.M., Ivanova Y.B., Maltseva O.V. J. Porphyrins Phthalocyanines 2009, 13, 1148–1158.
https://doi.org/10.1142/S1088424609001492

54. Gael V.I., Kuzmitsky V.A., Solovyov K.N. J. Appl. Spectrosc. 2000, 67, 696–702.
https://doi.org/10.1023/A:1004112102893

55. Haddad R.E.J., Gazeau S., Pecaut J., Marchon J.-C., Medforth C.J., Shelnutt J.A. J. Am. Chem. Soc. 2003, 125, 1253–1268.
https://doi.org/10.1021/ja0280933

56. Yamauchi S., Matsukawa Y., Ohba Y., Iwaizumi M. Inorg. Chem. 1996, 35, 2910–2914.
https://doi.org/10.1021/ic951108w

57. Liulkovich L.S., Kruk M.M. Trudy BGTU [Proceedings of Belarusian State Technological University (BSTU)]: Physics, mathematics and computer science. 2015, 170(6), 63–67 (in Russian).

58. Maes W., Amabilino D.B., Dehaen W. Tetrahedron 2003, 59, 3937–3943.
https://doi.org/10.1016/S0040-4020(03)00462-9

59. Chavan S.A., Maes W., Gevers L.E.M., Wahlen J., Vankelecom I.F.J., Jacobs P.A., Dehaen W., De Vos D.E. Chem. Eur. J. 2005, 11, 6754–6762.
https://doi.org/10.1002/chem.200500251

60. Maes W., Vanderhaeghen J., Smeets S., Asokan C.V., Van Renterghem L.M., Du Prez F.E., Smet M., Dehaen W. J. Org. Chem. 2006, 71, 2987–2994.
https://doi.org/10.1021/jo052534u

61. Maes W., Dehaen W. Eur. J. Org. Chem. 2009, 4719–4752.
https://doi.org/10.1002/ejoc.200900512

ESI

LeSaulnier T.D., Graham B.W., Geier III G.R. Tetrahedron Lett 2005, 46, 5633–5637

https://doi.org/10.1016/j.tetlet.2005.06.103

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Spectral-Luminescent Properties of meso-Tetraarylporphyrins Revisited: The Role of Aryl Type, Substitution Pattern and Macrocycle Core Protonation

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