Skip to main content
SpringerLink
Log in

The Effect of Substituent Position on Excited State Intramolecular Proton Transfer in Benzoxazinone Derivatives: Experiment and DFT Calculation

  • ORIGINAL ARTICLE
  • Published:
Journal of Fluorescence Aims and scope Submit manuscript

Abstract

The preparation and the photophysical behaviour of two benzoxazinone derivatives isomers 2-(1-hydroxynaphthalen-2-yl)-4H-benzo[e][1, 3]oxazin-4-one(1) and 2-(3-hydroxynaphthalen-2-yl)-4H-benzo[e][1, 3]oxazin-4-one(2) designed for displaying were reported. The effect of substituent position and solvent effect on the excited state intramolecular proton transfer (ESIPT) dynamics and the spectroscopic properties were investigated using a combined theoretical (i.e., time-dependent density function theory (DFT)) and experimental (i.e., steady-state absorption and emission spectra and time-resolved fluorescence spectra) study. The results showed that compound 1 would facilitate ESIPT process and favored the keto tautomer emission, while compound 2 suppressed the ESIPT process and favored the enol emission.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7

Similar content being viewed by others

References

  1. Abou-Zied OK, Jimenez R, Romesberg FE (2001) Tautomerization dynamics of a model base pair in DNA. J Am Chem Soc 123:4613–4614

    Article  CAS  PubMed  Google Scholar 

  2. Ray D, Paul BK, Guchhait N (2012) Effect of biological confinement on the photophysics and dynamics of a proton-transfer phototautomer: an exploration of excitation and emission wavelength-dependent photophysics of the protein-bound drug. Phys Chem Chem Phys 14:12182–12192

    Article  CAS  PubMed  Google Scholar 

  3. Lan X, Yang D, Sui X et al (2013) Time-dependent density functional theory (TD-DFT) study on the excited-state intramolecular proton transfer (ESIPT) in 2-hydroxybenzoyl compounds: significance of the intramolecular hydrogen bonding. Spectrochim Acta A 102:281–285

    Article  CAS  Google Scholar 

  4. Zhao J, Ji S, Chen Y, Guo H, Yang P (2012) Excited state intramolecular proton transfer (ESIPT): from principal photophysics to the development of new chromophores and applications in fluorescent molecular probes and luminescent materials. Phys Chem Chem Phys 14:8803–8817

    Article  CAS  PubMed  Google Scholar 

  5. Kwon JE, Park SY (2011) Advanced organic optoelectronic materials: harnessing excited-state intramolecular proton transfer (ESIPT) process. Adv Mater 23:3615–3642

    Article  CAS  PubMed  Google Scholar 

  6. Paterson MJ, Robb MA, Blancafort L, DeBellis AD (2005) Mechanism of an exceptional class of photostabilizers: a seam of conical intersection parallel to excited state intramolecular proton transfer (ESIPT) in o-hydroxyphenyl-(1, 3, 5)-triazine. J Phys Chem A 109:7527–7537

    Article  CAS  PubMed  Google Scholar 

  7. Sun W, Li S, Hu R, Qian Y, Wang S, Yang G (2009) Understanding solvent effects on luminescent properties of a triple fluorescent ESIPT compound and application for white light emission. J Phys Chem A 113:5888–5895

    Article  CAS  PubMed  Google Scholar 

  8. Klymchenko AS, Shvadchak VV, Yushchenko DA, Jain N, Mély Y (2008) Excited-state intramolecular proton transfer distinguishes microenvironments in single-and double-stranded DNA. J Phys Chem B 112:12050–12055

    Article  CAS  PubMed  Google Scholar 

  9. Weller A (1961) Fast reactions of excited molecules. Prog React Kinet 1:187

    CAS  Google Scholar 

  10. Lamola AA, Sharp LJ (1966) Environmental effects on the excited states of o-hydroxy aromatic carbonyl compounds. J Phys Chem 70:2634–2638

    Article  CAS  Google Scholar 

  11. Bader AN, Ariese F, Gooijer C (2002) Proton transfer in 3-hydroxyflavone studied by high-resolution 10 K laser-excited Shpol'skii spectroscopy. J Phys Chem A 106:2844–2849

    Article  CAS  Google Scholar 

  12. Schmidtke SJ, Underwood DF, Blank DA (2004) Following the solvent directly during ultrafast excited state proton transfer. J Am Chem Soc 126:8620–8621

    Article  CAS  PubMed  Google Scholar 

  13. Douhal A, Amat-Guerri F, Acuna AU (1995) Photoinduced intramolecular proton transfer and charge redistribution in imidazopyridines. J Phys Chem 99:76–80

    Article  CAS  Google Scholar 

  14. Piechowska J, Huttunen K, Wróbel Z, Lemmetyinen H, Tkachenko NV, Gryko DT (2012) Excited state intramolecular proton transfer in electron-rich and electron-poor derivatives of 10-Hydroxybenzo [h] quinoline. J Phys Chem A 116:9614–9620

    Article  CAS  PubMed  Google Scholar 

  15. Stasyuk AJ, Banasiewicz M, Cyrański MK, Gryko DT (2012) Imidazo [1, 2-a] pyridines susceptible to excited state intramolecular proton transfer: one-pot synthesis via an Ortoleva-King reaction. J Organomet Chem 77:5552–5558

    Article  CAS  Google Scholar 

  16. Shigemitsu Y, Mutai T, Houjou H, Araki K (2012) Excited-state intramolecular proton transfer (ESIPT) emission of hydroxyphenylimidazopyridine: computational study on enhanced and polymorph-dependent luminescence in the solid state. J Phys Chem A 116:12041–12048

    Article  CAS  PubMed  Google Scholar 

  17. Wu Y, Peng X, Fan J, Gao S, Tian M, Zhao J, Sun S (2007) Fluorescence sensing of anions based on inhibition of excited-state intramolecular proton transfer. J Organomet Chem 72:62–70

    Article  CAS  Google Scholar 

  18. Patil VS, Padalkar VS, Tathe AB, Gupta VD, Sekar N (2013) Synthesis, photo-physical and DFT studies of ESIPT inspired novel 2-(2′, 4′-dihydroxyphenyl) benzimidazole, benzoxazole and benzothiazole. J Fluoresc 23:1019–1029

    Article  CAS  PubMed  Google Scholar 

  19. Hadjoudis E, Mavridis IM (2004) Photochromism and thermochromism of Schiff bases in the solid state: structural aspects. Chem Soc Rev 33:579–588

    CAS  PubMed  Google Scholar 

  20. Jakobsen P, Horneman AM, Persson E (2000) Inhibitors of the tissue factor/factor VIIa-induced coagulation: synthesis and in vitro evaluation of novel 2-aryl substituted pyrido [3, 4-d][1, 3]-, pyrido [2, 3-d][1, 3]-, pyrazino [2, 3-d][1, 3]-, pyrimido [4, 5-d][1, 3]-, pyrazolo [3, 4-d][1, 3]-, thieno [3, 2-d][1, 3]-and thieno [2, 3-d][1, 3]-oxazin-4-ones. Bioorg Med Chem 8:2803–2812

    Article  CAS  PubMed  Google Scholar 

  21. Geigy J. R. A.-G. 2-Substituted-phenyl-4H-1,3-benzoxazin-4-ones[P]. GB: 1152980, 1969 5 21.

  22. Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery JA, Jr., Peralta JE, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam JM, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas Ö, Foresman JB, Ortiz JV, Cioslowski J, and Fox DJ (2009) Gaussion 09 Revision A.1. Gaussian Inc, Wallingford

  23. Gutierrez M, Alarcos N, Liras M, Sánchez F, Douhal A (2015) Switching to a reversible proton motion in a charge-transferred dye. J Phys Chem B 119:552–562

    Article  CAS  PubMed  Google Scholar 

  24. Nagaoka SI, Nagashima U (1989) Intramolecular proton transfer in various electronic states of o-hydroxybenzaldehyde. Chem Phys 136:153–163

    Article  CAS  Google Scholar 

  25. Nagaoka SI, Kusunoki J, Fujibuchi T, Hatakenaka S, Mukai K, Nagashima U (1999) Nodal-plane model of the excited-state intramolecular proton transfer of 2-(o-hydroxyaryl) benzazoles. J Photochem Photobiol A Chem 122:151–159

    Article  CAS  Google Scholar 

  26. Zhou P, Hoffmann MR, Han K, He G (2014) New insights into the dual fluorescence of methyl salicylate: effects of intermolecular hydrogen bonding and solvation. J Phys Chem B 119:2125–2131

    Article  PubMed  Google Scholar 

  27. Shynkar VV, Mely Y, Duportail G, Piémont E, Klymchenko AS, Demchenko AP (2003) Picosecond time-resolved fluorescence studies are consistent with reversible excited-state intramolecular proton transfer in 4'-(dialkylamino)-3-hydroxyflavones. J Phys Chem A 107:9522–9529

    Article  CAS  Google Scholar 

  28. Borst DR, Roscioli JR, Pratt DW, Florio GM, Zwier TS, Müller A, Leutwyler S (2002) Hydrogen bonding and tunneling in the 2-pyridone· 2-hydroxypyridine dimer. Effect Electro Excitation Chem Phys 283:341–354

    CAS  Google Scholar 

  29. Tautermann CS, Voegele AF, Liedl KR (2003) The ground state tunneling splitting of the 2-pyridone· 2-hydroxypyridine dimer. Chem Phys 292:47–52

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The authors gratefully thank the support from International S&T Cooperation Program of China (2012DFA51210), National Natural Science Foundation of China (51203138, 51273179, 51573165), Natural Science Foundation of Zhejiang Province, China (LY15E030006) and Natural Science Foundation of Zhejiang University of Technology (1401101002408).

Author information

Authors and Affiliations

  1. College of Chemical Engineering, Zhejiang University of Technology, Hangzhou, 310014, People’s Republic of China

    Gao-Feng Bian, Yun Guo, Xiao-Jing Lv & Cheng Zhang

  2. Key Laboratory of Organosilicon Chemistry and Material Technology, Hangzhou Normal University, Hangzhou, 311121, People’s Republic of China

    Gao-Feng Bian

Authors
  1. Gao-Feng Bian
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Yun Guo
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Xiao-Jing Lv
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Cheng Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Cheng Zhang.

Supplementary material

See supplementary material for the calculated structures cartesian coordinates of 1 and 2 and corresponding fitting parameters of the time-resolved fluorescence for 1 and 2. (DOCX 73 kb)

ESM 1

(DOCX 73 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Bian, GF., Guo, Y., Lv, XJ. et al. The Effect of Substituent Position on Excited State Intramolecular Proton Transfer in Benzoxazinone Derivatives: Experiment and DFT Calculation. J Fluoresc 27, 235–242 (2017). https://doi.org/10.1007/s10895-016-1950-9

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10895-016-1950-9

Keywords

Search

Navigation