Singlet excited state dipole moments of dual fluorescent N-phenylpyrroles and 4-(dimethylamino)benzonitrile from solvatochromic and thermochromic spectral shifts

Photochemical and Photobiological Sciences

Volumn 2, Issue 3, 2003, Pages 342-353

  Yoshihara, Toshitada ^a,b   Galievsky, Victor A ^a   Druzhinin, Sergey I ^a   Saha, Satyen ^a,c   Zachariasse, Klaas A ^a  

^a MAX PLANCK INSTITUTE FOR BIOPHYSICAL CHEMISTRY   (Germany)

^b NATIONAL INSTITUTE OF ADVANCED INDUSTRIAL SCIENCE AND TECHNOLOGY AIST   (Japan)

^c UNIVERSITY OF HYDERABAD   (India)

Author keywords

[No Author keywords available]

Indexed keywords

1 PHENYLPYRROLE; 4 (DIMETHYLAMINO)BENZONITRILE; AMINOBENZONITRILE; BENZENE DERIVATIVE; BENZONITRILE; CYANIDE; ETHER; N (3 CYANOPHENYL)PYROLE; N (4 CYANOPHENYL)PYRROLE; N (4 METHYLPHENYL)PYRROLE; N PROPYL CYANIDE; NITRILE; PYRROLE DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL ANALYSIS; DIPOLE; FLUORESCENCE; MATERIAL STATE; PRIORITY JOURNAL; PROTON NUCLEAR MAGNETIC RESONANCE;

EID: 0344810166     PISSN: 1474905X     EISSN: 14749092     Source Type: Journal    
DOI: 10.1039/b211838f     Document Type: Article

References (46)

1. W. Rettig and F. Marschner, Population of excited charge transfer states and molecular conformation in N-phenylpyrroles, Nouv. J. Chim., 1983, 7, 425-431.
2. W. Rettig, Charge separation in excited states of decoupled systems-TICT compounds and implications regarding the development of new laser dyes and the primary processes of vision and photosynthesis, Angew. Chem., Int. Ed. Engl., 1986, 25, 971-988.
3. W. Rettig and F. Marschner, Molecular conformation and biradicaloid charge transfer states in substituted N-phenylpyrroles, New. J. Chem., 1990, 14, 819-824.
4. See the remark on the meaning of LE in ref. 5.
5. K. A. Zachariasse, T. Yoshihara and S. I. Druzhinin, Picosecond and nanosecond fluorescence decays of 4-(dimethylamino)-phenylacetylene in comparison with those of 4-(dimethylamino)-benzonitrile. No evidence for intramolecular charge transfer and a nonfluorescing intramolecular charge transfer state, J. Phys. Chem. A, 2002, 106, 6325-6333;
6. See correction in J. Phys. Chem. A, 2002, 106, 8978.
7. A. Sarkar and S. Chakravorti, A study on the spectroscopy and photophysics of N-phenyl pyrrole and N-phenyl pyrazole, Chem. Phys. Lett., 1995, 235, 195-201.
8. J. Manz, B. Proppe and B. Schmidt, Time-resolved dual fluorescence of 1-phenylpyrrole in acetonitrile: molecular dynamics simulations of solvent response to twisted intramolecular charge transfer, Phys. Chem. Chem. Phys., 2002, 4, 1876-1881.
9. C. Cornelissen-Gude and W. Rettig, Dual fluorescence and multiple charge transfer nature in derivatives of N-pyrrolobenzonitrile, J. Phys. Chem. A, 1998, 102, 7754-7760.
10. W. Rettig, Application of a simplified microstructural solvent interaction model to the solvatochromism of twisted intramolecular charge transfer, J. Mol. Struct., 1982, 84, 303-327.
11. e(ICT) = 22.4 D. The ICT dipole moment of PP4C was found in ref. 9 to be larger than that of DMABN (12.2 D with ρ = 5.00 Å).
12. C. Cazeau-Dubroca, A. Peirigua, S. Ait Lyazidi, G. Nouchi, Ph. Cazeau and R. Lapouyade, TICT fluorescence in rigid matrices: α-delayed fluorescence, Chem. Phys. Lett., 1986, 124, 110-115.
13. K. Okuyama, Y. Numata, S. Odawara and I. Suzuka, Electronic spectra of jet-cooled I-phenylpyrrole: large amplitude torsional motion and twisted intramolecular charge-transfer phenomena, J. Chem. Phys., 1998, 109, 7185-7195.
14. L. Belau, Y. Haas and W. Rettig, Jet cooled spectra of pyrrolobenzene and of pyrrolobenzonitrile: the nature of the excited states, Chem. Phys. Lett., 2002, 364, 157-163.
15. H. Okamoto and M. Kinoshita, Picosecond infrared spectrum of 4-(pyrrol-1-yl)benzonitrile: structure of the excited charge-transfer states of donor-acceptor systems, J. Phys. Chem. A, 2002, 106, 3485-3490.
16. th IUPAC Symposium on Photochemistry, Sitges, 1998, p. 75.
17. B. Proppe, M. Merchán and L. Serrano-Andrés, Theoretical study of the twisted intramolecular charge transfer in 1-phenylpyrrole, J. Phys. Chem. A, 2000, 104, 1608-1616.
18. A. B. J. Parusel, A DFT/MRCI study on the excited state charge transfer states of N-pyrrolobenzene, N-pyrrolobenzonitrile and 4-N,N- dimelhylaminobenzonitrile, Phys. Chem. Chem. Phys., 2000, 2, 5545-5552.
19. The equation employed in ref. 17 to estimate the solvent stabilisation is different from that used here, cf. eqns. (1)-(4).
20. S. Zilberg and Y. Haas, The nature of the intramolecular charge transfer excited state in p-pyrrolocyanobenzene (PBN) and other derivatives of benzene substituted by electron donor and acceptor groups, J. Phys. Chem. A, 2002, 106, 1-11.
21. K. A. Zachariasse, M. Grobys, Th. von der Haar, A. Hebecker, Yu. V. Il'ichev, Y.-B. Jiang, O. Morawski and W. Kühnle, Intramolecular charge transfer in the excited state. Kinetics and configurational changes, J. Photochem. Photobiol. A, 1996, 102, 59-70.
22. K. A. Zachariasse, The PICT model for dual fluorescence of aminobenzonitriles, Chem. Phys. Lett., 2000, 320, 8-13.
23. Z. R. Grabowski, K. Rotkiewicsz, A. Siemiarczuk, D. J. Cowley and W. Baumann, Twisted intramolecular charge transfer states (TICT). A new class of excited states with a full charge separation, Nouv. J. Chim., 1979, 3, 443-454.
24. J. B. Birks, Photophysics of Aromatic Molecules, Wiley, London, 1970.
25. K. A. Zachariasse, M. Grobys and E. Tauer, Absence of dual fluorescence with 4-(dimethylamino)phenylacetylene. A comparison between experimental results and theoretical predictions, Chem. Phys. Lett., 1997, 274, 372-382.
26. W. Schuddeboom, S. A. Jonker, J. M. Warman, U. Leinhos, W. Kühnle and K. A. Zachariasse, Excited-state dipole moments of dual fluorescent 4-(dialkylamino)benzonitriles. Influence of alkyl chain length and effective solvent polarity, J. Phys. Chem., 1992, 96, 10809-10819.
27. Yu. V. Il'ichev, W. Kühnle and K. A. Zachariasse, Photophysics of 4-dimethylamino-4′-cyanostilbene and 4-azetidinyl-4′-cyanostilbene. Time-resolved fluorescence and trans-cis photoisomerisation, Chem. Phys., 1996, 211, 441-453.
28. W. Liptay, Dipole moments and polarizabilities of molecules in excited electronic states, in Excited States, vol. 1, ed. E. C. Lim, Academic Press, New York, 1974, p. 129.
29. W. Baumann, H. Bischof, J.-C. Fröhling, C. Brittinger, W. Rettig and K. Rotkiewicz, Considerations on the dipole moment of molecules forming the twisted intramolecular charge transfer state, J. Photochem. Photobiol. A, 1992, 64, 49-72.
30. A. Heine, R. Herbst-Irmer, D. Stalke, W. Kühnle and K. A. Zachariasse, Structure and crystal packing of 4-amino-benzonitriles and 4-amino-3,5-dimethylbenzonitriles at various temperatures, Acta Crystallogr., Sect. B, 1994, 50, 363-371.
31. D. Stalke, R. von Bülow and K. A. Zachariasse, unpublished results.
32. A. Demeter, S. Druzhinin, M. George, E. Haselbach, J.-L. Roulin and K. A. Zachariasse, Dual fluorescence and fast intramolecular charge transfer with 4-(diisopropylamino)benzonitrile in alkane solvents, Chem. Phys. Lett., 2000, 323, 351-360.
33. P. Suppan N. Ghoneim, Solvatochromism, The Royal Society of Chemistry, Cambridge, UK, 1997, ch. 9.
34. H. Beens and A. Weller, Characteristics of molecular complexes in the excited state, Acta Phys. Pol., 1968, 34, 593-542.
35. H. Lumbroso, D. M. Bertin and F. Marschner, A dipole moment study of gradually hindered N-phenylpyrroles, J. Mol. Struct., 1988, 178, 187-200.
36. M. W. Schmidt, K. K. Baldridge, J. A. Boatz, S. T. Elbert, M. S. Gordon, J. H. Jensen, S. Koseki, N. Matsunaga, K. A. Nguyen, S. J. Su, T. L. Windus, M. Dupuis and J. A. Montgomery, General atomic and molecular electronic-structure system (Gamess), J. Comput. Chem., 1993, 14, 1347-1363.
37. P. Suppan, Temperature effects in solvatochromic shifts, J. Chem. Soc., Faraday Trans. 2, 1981, 77, 1553-1562.
38. P. Suppan, Thermochromic shifts of the fluorescence spectra of 4-N,N-dimethylaminobenzonitrile in solution, J. Lumin., 1985, 33, 29-32.
39. T. Hagan, D. Pilloud and P. Suppan, Thermochromic shifts of some molecular and exciplex fluorescence spectra, Chem. Phys. Lett., 1987, 139, 499-502.
40. P. Suppan, Solvatochromic shifts: the influence of the medium on the energy of electronic states, J. Photochem. Photobiol. A, 1990, 50, 293-330.
41. A. Kawski and W. Kolakowski, Über die Temperaturabhängigkeit der Absorptions- und Fluoreszenzspektren von 4-Amino-phthalimid, Acta Phys. Pol., 1966, 29, 177-186.
42. I. Gryczynski and A. Kawski, Temperaturabhängigkeit der statischen Dielektrizitätskonstante und des optischen Brechungsindexes von Flüssigkeiten, Z. Naturforsch., 1975, 30A, 287-291.
43. W. Rettig, D. Braun, P. Suppan, E. Vauthey, K. Rotkiewicsz, R. Luboradzki and K. Suwińska, Molecular conformation and excited-state dipole moments of di- and tetramethylaminobenzonitrile (DMABN and TMABN), J. Phys. Chem., 1993, 97, 13500-13507.
44. Landolt-Börnstein, Numerical Data and Functional Relationships in Science and Technology, New Series, ed. O. Madelung, Group IV, volume 6, Springer, Berlin, 1991.
45. Landolt-Börnstein, Numerical Data and Functional Relationships in Science and Technology, New Series, ed. M. D. Lechner, Group III, volume 38B, Springer, Berlin, 1996.
46. th edition, Wiley, New York, 1986.