Journal of Molecular Modeling

, Volume 18, Issue 3, pp 963–972 | Cite as

Theoretical study of crown ethers with incorporated azobenzene moiety

Original Paper
First Online:
Received:
Accepted:

Abstract

A series of crown ethers containing the azobenzene moiety incorporated into crowns of various sizes [Cr(O6), Cr(O7) and Cr(O8)] and their corresponding alkali metal cation (Li+, Na+, K+, Rb+) complexes have been studied theoretically. The density functional theory (DFT) method was employed to elucidate the stereochemical structural natures and thermodynamic properties of all of the target molecules at the B3LYP/6-31 G(d) and LANL2DZ level for the cation Rb+. The fully optimized geometries had real frequencies, thus indicating their minimum-energy status. In addition, the bond lengths between the metal cation and oxygen atoms, atomic torsion angles and thermodynamic energies for complexes were studied. Natural bond orbital (NBO) analysis was used to explore the origin of the internal forces and the intermolecular interactions for the metal complexes. The calculated results show that the most significant interaction is that between the lone pair electrons of electron-donating oxygens in the cis-forms of azobenzene crown ethers (cis-ACEs) and the LP* (1-center valence antibond lone pair) orbitals of the alkali-metal cations (Li+, Na+, K+ and Rb+). The electronic spectra for the cis-ACEs [cis-Cr(O6), cis-Cr(O7) and cis-Cr(O8)] are obtained by the time-dependent density functional theory (TDDFT) at the B3LYP/6-31 G(d) level. The spectra of the cis-isomers show broad π → π* (S0 → S2) absorption bands at 310–340 nm but weaker n → π* (S0 → S1) bands at 480–490 nm. The calculated results are in good agreement with the experimental results.

Figure

A series of crown ethers containing the azobenzene moiety incorporated into crowns of various sizes [Cr(O6), Cr(O7) and Cr(O8)] and their corresponding alkali metal cation (Li+, Na+, K+, Rb+) complexes were studied theoretically

Keywords

Azobenzene crown ethers (ACEs) Photoisomerization Preorganization Switchable molecules Time-dependent density functional theory (TDDFT) 
This is a preview of subscription content, log in to check access.

Notes

Acknowledgments

The author wish to acknowledge the financial support from the Scientific Research Fund of Hunan Provincial Education Department (no. 09A091).

References

  1. 1.
    Kyba EP, Helgeson RC, Madan K, Gokel GW, Tarnowski TL, Moore SS, Cram DJ (1977) J Am Chem Soc 99:2564–2571Google Scholar
  2. 2.
    Kovbasyuk L, Krämer R (2004) Chem Rev 104:3161–3187CrossRefGoogle Scholar
  3. 3.
    Pedersen CJ (1967) J Am Chem Soc 89:7017–7036CrossRefGoogle Scholar
  4. 4.
    Gokel GW (1991) Crown ethers and cryptands. Royal Society of Chemistry, CambridgeGoogle Scholar
  5. 5.
    More MB, Glendening ED, Ray D, Feller D, Armentrout PB (1996) J Phys Chem 100:1605–1614CrossRefGoogle Scholar
  6. 6.
    Feringa BL (2001) Molecular switches. Wiley-VCH, Weinheim, p 454Google Scholar
  7. 7.
    Balzani V, Scandola F (1991) Supramolecular photochemistry. Ellis Horwood, New York, pp 199–215Google Scholar
  8. 8.
    Liu ZF, Hashimoto K, Fujishima A (1990) Nature 347:658–660CrossRefGoogle Scholar
  9. 9.
    Ikeda T, Tsutsumi O (1995) Science 268:1873–1875CrossRefGoogle Scholar
  10. 10.
    Sekkat Z, Dumont M (1992) Appl Phys B 54:486–489CrossRefGoogle Scholar
  11. 11.
    Hugel T, Holland NB, Cattani A, Moroder L, Seitz M, Gaub HE (2002) Science 296:1103–1106CrossRefGoogle Scholar
  12. 12.
    Muraoka T, Kinbara K, Kobayashi Y, Aida T (2003) J Am Chem Soc 125:5612–5613CrossRefGoogle Scholar
  13. 13.
    Zhang C, Du MH, Cheng HP, Zhang XG, Roitberg AE, Krause JL (2004) Phys Rev Lett 92:158301(1–4)Google Scholar
  14. 14.
    Halabieh HE, Mermut O, Barrett CJ (2004) Pure Appl Chem 76:1445–1465CrossRefGoogle Scholar
  15. 15.
    Shinkai S, Nakaji T, Nishida Y, Ogawa T, Manabe O (1980) J Am Chem Soc 102:5860–5865CrossRefGoogle Scholar
  16. 16.
    Tahara R, Morozumi T, Nakamura H, Shimomura M (1997) J Phys Chem B 101:7736–7743CrossRefGoogle Scholar
  17. 17.
    Shinkai S, Minami T, Kusano Y, Manabe O (1983) J Am Chem Soc 105:1851–1856CrossRefGoogle Scholar
  18. 18.
    Becke AD (1993) J Chem Phys 98:5648–5652CrossRefGoogle Scholar
  19. 19.
    Lee C, Yang W, Parr RG (1988) Phys Rev B 37:785–789CrossRefGoogle Scholar
  20. 20.
    Korth HG, De Heer MI, Mulder P (2002) J Phys Chem A 106:8779–8789CrossRefGoogle Scholar
  21. 21.
    Johnson BG, Gill PMW, Pople JA (1993) J Chem Phys 98:5612–5626CrossRefGoogle Scholar
  22. 22.
    Chowdhury PK (2003) J Phys Chem A 107:5692–5696CrossRefGoogle Scholar
  23. 23.
    Chis V (2004) Chem Phys 300:1–11CrossRefGoogle Scholar
  24. 24.
    Asensio A, Kobko N, Dannenberg JJ (2003) J Phys Chem A 107:6441–6443CrossRefGoogle Scholar
  25. 25.
    Müller A, Losada M, Leutwyler S (2004) J Phys Chem A 108:157–165CrossRefGoogle Scholar
  26. 26.
    Goncalves NS, Cristiano R, Pizzolatti MG, da Silva Miranda F (2005) J Mol Struct 733:53–61Google Scholar
  27. 27.
    Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Montgomery JAJr, Vreven T, Kudin KN, Burant JC, Millam JM, Iyengar SS, Tomasi J, Barone V, Mennucci B, Cossi M, Scalmani G, Rega N, Petersson GA, Nakatsuji H, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Klene M, Li X, Knox JE, Hratchian HP, Cross JB, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Ayala PY, Morokuma K, Voth GA, Salvador P, Dannenberg JJ, Zakrzewski VG, Dapprich S, Daniels AD, Strain MC, Farkas O, Malick DK, Rabuck AD, Raghavachari K, Foresman JB, Ortiz JV, Cui Q, Baboul AG, Clifford S, Cioslowski J, Stefanov BB, Liu G, Liashenko A, Piskorz P, Komaromi I, Martin RL, Fox DJ, Keith TM, Al-Laham A, Peng CY, Nanayakkara A, Challacombe MP, Gill MW, Johnson B, Chen W, Wong MW, Gonzalez C, Pople JA (2003) Gaussian 2003W, revision B.05. Gaussian Inc., PittsburghGoogle Scholar
  28. 28.
    Reed AE, Curtiss LA, Weinhold F (1988) Chem Rev 88:899–926CrossRefGoogle Scholar
  29. 29.
    Reed AE, Weinhold F (1983) J Chem Phys 78:4066–4073CrossRefGoogle Scholar
  30. 30.
    Foster JP, Weinhold F (1980) J Am Chem Soc 102:7211–7218CrossRefGoogle Scholar
  31. 31.
    Reed AE, Weinstock RB, Weinhold F (1985) J Chem Phys 83:735–746CrossRefGoogle Scholar
  32. 32.
    Schulze FW, Petrick HJ, Cammenga HK, Klinge H (1977) Z Phys Chem Neue Fol 107:4743Google Scholar
  33. 33.
    Cattaneo P, Persico M (1999) Phys Chem Chem Phys 1:4739–4743CrossRefGoogle Scholar
  34. 34.
    Ishikawa T, Noro T, Shoda TJ (2001) Chem Phys 115:7503–7512Google Scholar
  35. 35.
    Tiago ML, Ismail-Beigi S, Louie SG (2005) J Chem Phys 122:094311(1–7)Google Scholar
  36. 36.
    Cembran A, Bernardi F, Garavelli L, Gagliardi L, Orlandi G (2004) J Am Chem Soc 126:3234–3243CrossRefGoogle Scholar
  37. 37.
    Biswas N, Umpathy S (1997) J Phys Chem 107:7849–7858CrossRefGoogle Scholar
  38. 38.
    Mostad A, Romming C (1971) Acta Chem Scand 25:3561–3568CrossRefGoogle Scholar
  39. 39.
    Fliegl H, Kohn A, Hattig C, Ahlrichs R (2003) J Am Chem Soc 125:9821–9827CrossRefGoogle Scholar
  40. 40.
    Hopkins HP Jr, Norman AB (1980) J Phys Chem 84:309–314CrossRefGoogle Scholar
  41. 41.
    Smetana AJ, Popov AI (1980) J Solution Chem 9:183–196CrossRefGoogle Scholar
  42. 42.
    Lamb JD, Izatt RM, Swain CS, Christensen JJ (1980) J Am Chem Soc 102:475–479CrossRefGoogle Scholar
  43. 43.
    Ouchi M, Inoue Y, Kanzaki T, Hakushi T (1984) J Org Chem 49:1408–1412CrossRefGoogle Scholar
  44. 44.
    Pedersen C (1970) J Am Chem Soc 92:391–394CrossRefGoogle Scholar
  45. 45.
    Liu Y, Lu TB, Tan MY, Hakushi T, Inoue Y (1993) J Phys Chem 97:4548–4551Google Scholar
  46. 46.
    Ouchi M, Inoue Y (1985) Bull Chem Soc Jpn 58:525–530CrossRefGoogle Scholar
  47. 47.
    Ouchi M, Inoue Y, Kanzaki T (1984) Bull Chem Soc Jpn 57:887–888CrossRefGoogle Scholar
  48. 48.
    Hill SE, Feller D (2000) Int J Mass Spectrom 201:41–58CrossRefGoogle Scholar
  49. 49.
    Adamovic I, Gordon MS (2005) J Phys Chem A 109:1629–1636CrossRefGoogle Scholar
  50. 50.
    Mo Y, Wu W, Song L, Lin M, Zhang Q, Gao J (2004) Angew Chem Int Ed 43:1986–1990Google Scholar
  51. 51.
    Mo Y, Jiao H, Schleyer PvR (2004) J Org Chem 69:3493–3499CrossRefGoogle Scholar
  52. 52.
    Mo Y, Schleyer PvR, Wu W, Lin M, Zhang Q, Gao J (2003) J Phys Chem A 107:10011–10018CrossRefGoogle Scholar
  53. 53.
    Cramer CJ (2002) Essentials of computational chemistry: theories and models, 2nd edn. Wiley, New YorkGoogle Scholar
  54. 54.
    Kim KS, Tarakeshwar P, Lee JY (2000) Chem Rev 100:4145–4186CrossRefGoogle Scholar
  55. 55.
    Boys SF, Bernardi F (1970) Mol Phys 19:553–566CrossRefGoogle Scholar
  56. 56.
    Crecca CR, Roitberg AE (2006) J Phys Chem A 110:8188–8203CrossRefGoogle Scholar
  57. 57.
    Nägele T, Hoche R, Zinth W, Wachtveitl J (1997) Chem Phys Lett 272:489–495CrossRefGoogle Scholar

Copyright information

© Springer-Verlag 2011

Authors and Affiliations

  1. 1.Key Laboratory of Environmentally Friendly Chemistry and Applications of Ministry of Education, College of ChemistryXiangtan UniversityXiangtanPeople’s Republic of China

Personalised recommendations