Excited state intramolecular proton transfer (ESIPT) is a process in which photoexcited molecules relax their energy through tautomerization by transfer of protons. Some kinds of molecules could have different minimum-energy tautomers in different electronic states, and if the molecular structure of minimum-energy tautomer in the excited state is proton-transferred geometry between neighboring atoms, proton transfer in excited state can occur. The tautomerization often takes the form of keto-enol tautomerism.
CharacteristicEdit
Since a proton-transferred geometry is usually the minimum-energy tautomer only in the excited state and relatively unstable in the ground state, molecules that have ESIPT character may show extraordinarily larger Stokes shift than common fluorescent molecules, or exhibit dual fluorescence that shorter-wavelength one comes from the original tautomer and longer-wavelength one from proton-transferred tautomer.[1][2] However, there are some exceptional cases where ESIPT molecules have no dual luminescence or significantly red-shifted emission from proton-transferred tautomer, from various reasons.[3][4][5]
Rate of ESIPT process may slow down by deuterium substitution of hydrogen that is transferred in ESIPT, because the deuteration increases only mass of the transferred significantly while do not change electrostatic potential in the molecule substantially.[6] However the amount of rate change may lie in the range of 1~50, depending on the shape and size of potential energy surfaces of the molecule.[7]
ApplicationEdit
Based on characteristic that molecules usually have extraordinarily larger Stokes shift when ESIPT occurs, various applications have been developed using red-shifted fluorescence. Applications include turn-on photoluminescence sensor,[8]photochromic, non-destructive optical memory,[9] and white-light emitting materials.[10]
Because phenol does not form a ketal under normal conditions because it does not tautomerize to any useful extent; however under ESIPT in the presence of an alcohol, e.g. ethylene glycol, it became possible to trap 1,4-Dioxaspiro[4.5]deca-6,8-diene [23783-59-7].
ReferencesEdit
^Joshi, Hem; Antonov, Liudmil (2021). "Excited-State Intramolecular Proton Transfer: A Short Introductory Review". Molecules. 26 (5): 1475. doi:10.3390/molecules26051475. PMC7963178.
^Zhao, Jianzhang; Ji, Shaomin; Chen, Yinghui; Guo, Huimin; Yang, Pei (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 (25): 8803–8817. Bibcode:2012PCCP...14.8803Z. doi:10.1039/C2CP23144A. PMID 22193300.
^Yin, Hang; Li, Hui; Xia, Guomin; Ruan, Chengyan; Shi, Ying; Wang, Hongming; Jin, Mingxing; Ding, Dajun (21 January 2016). "A novel non-fluorescent excited state intramolecular proton transfer phenomenon induced by intramolecular hydrogen bonds: an experimental and theoretical investigation". Scientific Reports. 6 (1): 19774. Bibcode:2016NatSR...619774Y. doi:10.1038/srep19774. PMC4726414. PMID 26790961.
^Han, Gi Rim; Hwang, Doyk; Lee, Seunghoon; Lee, Jong Woo; Lim, Eunhak; Heo, Jiyoung; Kim, Seong Keun (20 June 2017). "Shedding new light on an old molecule: quinophthalone displays uncommon N-to-O excited state intramolecular proton transfer (ESIPT) between photobases". Scientific Reports. 7 (1): 3863. Bibcode:2017NatSR...7.3863H. doi:10.1038/s41598-017-04114-9. PMC5478638. PMID 28634405.
^English, D. S.; Zhang, W.; Kraus, G. A.; Petrich, J. W. (April 1997). "Excited-State Photophysics of Hypericin and Its Hexamethoxy Analog: Intramolecular Proton Transfer as a Nonradiative Process in Hypericin". Journal of the American Chemical Society. 119 (13): 2980–2986. doi:10.1021/ja962476h.
^Flom, Steven R.; Barbara, Paul F. (October 1985). "Proton transfer and hydrogen bonding in the internal conversion of S1 anthraquinones". The Journal of Physical Chemistry. 89 (21): 4489–4494. doi:10.1021/j100267a017.
^Agmon, Noam (January 2005). "Elementary Steps in Excited-State Proton Transfer". The Journal of Physical Chemistry A. 109 (1): 13–35. doi:10.1021/jp047465m. PMID 16839085.
^Chen, Wei-Hua; Xing, Yu; Pang, Yi (18 March 2011). "A Highly Selective Pyrophosphate Sensor Based on ESIPT Turn-On in Water". Organic Letters. 13 (6): 1362–1365. doi:10.1021/ol200054w. PMID 21338073.
^Lim, Seon-Jeong; Seo, Jangwon; Park, Soo Young (November 2006). "Photochromic Switching of Excited-State Intramolecular Proton-Transfer (ESIPT) Fluorescence: A Unique Route to High-Contrast Memory Switching and Nondestructive Readout". Journal of the American Chemical Society. 128 (45): 14542–14547. doi:10.1021/ja0637604. PMID 17090038.
^Park, Sanghyuk; Kwon, Ji Eon; Kim, Se Hun; Seo, Jangwon; Chung, Kyeongwoon; Park, Sun-Young; Jang, Du-Jeon; Medina, Begoña Milián; Gierschner, Johannes; Park, Soo Young (7 October 2009). "A White-Light-Emitting Molecule: Frustrated Energy Transfer between Constituent Emitting Centers". Journal of the American Chemical Society. 131 (39): 14043–14049. doi:10.1021/ja902533f. PMID 19480450.
October 20, 2023
excited, state, intramolecular, proton, transfer, esipt, process, which, photoexcited, molecules, relax, their, energy, through, tautomerization, transfer, protons, some, kinds, molecules, could, have, different, minimum, energy, tautomers, different, electron. Excited state intramolecular proton transfer ESIPT is a process in which photoexcited molecules relax their energy through tautomerization by transfer of protons Some kinds of molecules could have different minimum energy tautomers in different electronic states and if the molecular structure of minimum energy tautomer in the excited state is proton transferred geometry between neighboring atoms proton transfer in excited state can occur The tautomerization often takes the form of keto enol tautomerism Characteristic EditSince a proton transferred geometry is usually the minimum energy tautomer only in the excited state and relatively unstable in the ground state molecules that have ESIPT character may show extraordinarily larger Stokes shift than common fluorescent molecules or exhibit dual fluorescence that shorter wavelength one comes from the original tautomer and longer wavelength one from proton transferred tautomer 1 2 However there are some exceptional cases where ESIPT molecules have no dual luminescence or significantly red shifted emission from proton transferred tautomer from various reasons 3 4 5 Rate of ESIPT process may slow down by deuterium substitution of hydrogen that is transferred in ESIPT because the deuteration increases only mass of the transferred significantly while do not change electrostatic potential in the molecule substantially 6 However the amount of rate change may lie in the range of 1 50 depending on the shape and size of potential energy surfaces of the molecule 7 Application EditBased on characteristic that molecules usually have extraordinarily larger Stokes shift when ESIPT occurs various applications have been developed using red shifted fluorescence Applications include turn on photoluminescence sensor 8 photochromic non destructive optical memory 9 and white light emitting materials 10 Because phenol does not form a ketal under normal conditions because it does not tautomerize to any useful extent however under ESIPT in the presence of an alcohol e g ethylene glycol it became possible to trap 1 4 Dioxaspiro 4 5 deca 6 8 diene 23783 59 7 References Edit Joshi Hem Antonov Liudmil 2021 Excited State Intramolecular Proton Transfer A Short Introductory Review Molecules 26 5 1475 doi 10 3390 molecules26051475 PMC 7963178 Zhao Jianzhang Ji Shaomin Chen Yinghui Guo Huimin Yang Pei 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 25 8803 8817 Bibcode 2012PCCP 14 8803Z doi 10 1039 C2CP23144A PMID 22193300 Yin Hang Li Hui Xia Guomin Ruan Chengyan Shi Ying Wang Hongming Jin Mingxing Ding Dajun 21 January 2016 A novel non fluorescent excited state intramolecular proton transfer phenomenon induced by intramolecular hydrogen bonds an experimental and theoretical investigation Scientific Reports 6 1 19774 Bibcode 2016NatSR 619774Y doi 10 1038 srep19774 PMC 4726414 PMID 26790961 Han Gi Rim Hwang Doyk Lee Seunghoon Lee Jong Woo Lim Eunhak Heo Jiyoung Kim Seong Keun 20 June 2017 Shedding new light on an old molecule quinophthalone displays uncommon N to O excited state intramolecular proton transfer ESIPT between photobases Scientific Reports 7 1 3863 Bibcode 2017NatSR 7 3863H doi 10 1038 s41598 017 04114 9 PMC 5478638 PMID 28634405 English D S Zhang W Kraus G A Petrich J W April 1997 Excited State Photophysics of Hypericin and Its Hexamethoxy Analog Intramolecular Proton Transfer as a Nonradiative Process in Hypericin Journal of the American Chemical Society 119 13 2980 2986 doi 10 1021 ja962476h Flom Steven R Barbara Paul F October 1985 Proton transfer and hydrogen bonding in the internal conversion of S1 anthraquinones The Journal of Physical Chemistry 89 21 4489 4494 doi 10 1021 j100267a017 Agmon Noam January 2005 Elementary Steps in Excited State Proton Transfer The Journal of Physical Chemistry A 109 1 13 35 doi 10 1021 jp047465m PMID 16839085 Chen Wei Hua Xing Yu Pang Yi 18 March 2011 A Highly Selective Pyrophosphate Sensor Based on ESIPT Turn On in Water Organic Letters 13 6 1362 1365 doi 10 1021 ol200054w PMID 21338073 Lim Seon Jeong Seo Jangwon Park Soo Young November 2006 Photochromic Switching of Excited State Intramolecular Proton Transfer ESIPT Fluorescence A Unique Route to High Contrast Memory Switching and Nondestructive Readout Journal of the American Chemical Society 128 45 14542 14547 doi 10 1021 ja0637604 PMID 17090038 Park Sanghyuk Kwon Ji Eon Kim Se Hun Seo Jangwon Chung Kyeongwoon Park Sun Young Jang Du Jeon Medina Begona Milian Gierschner Johannes Park Soo Young 7 October 2009 A White Light Emitting Molecule Frustrated Energy Transfer between Constituent Emitting Centers Journal of the American Chemical Society 131 39 14043 14049 doi 10 1021 ja902533f PMID 19480450 Retrieved from https en wikipedia org w index php title Excited state intramolecular proton transfer amp oldid 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