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Excited-state intramolecular proton transfer molecules bearing o-hydroxy analogues of green fluorescent protein chromophore.
J Org Chem. 2011 Oct 21; 76(20):8189-202.JO

Abstract

o-Hydroxy analogues, 1a-g, of the green fluorescent protein chromophore have been synthesized. Their structures and electronic properties were investigated by X-ray single-crystal analyses, electrochemistry, and luminescence properties. In solid and nonpolar solvents 1a-g exist mainly as Z conformers that possess a seven-membered-ring hydrogen bond and undergo excited-state intramolecular proton transfer (ESIPT) reactions, resulting in a proton-transfer tautomer emission. Fluorescence upconversion dynamics have revealed a coherent type of ESIPT, followed by a fast vibrational/solvent relaxation (<1 ps) to a twisted (regarding exo-C(5)-C(4)-C(3) bonds) conformation, from which a fast population decay of a few to several tens of picoseconds was resolved in cyclohexane. Accordingly, the proton-transfer tautomer emission intensity is moderate (0.08 in 1e) to weak (∼10(-4) in 1a) in cyclohexane. The stronger intramolecular hydrogen bonding in 1g suppresses the rotation of the aryl-alkene bond, resulting in a high yield of tautomer emission (Φ(f) ≈ 0.2). In the solid state, due to the inhibition of exo-C(5)-C(4)-C(3) rotation, intense tautomer emission with a quantum yield of 0.1-0.9 was obtained for 1a-g. Depending on the electronic donor or acceptor strength of the substituent in either the HOMO or LUMO site, a broad tuning range of the emission from 560 (1g) to 670 nm (1a) has been achieved.

Authors+Show Affiliations

Department of Chemistry, National Taiwan University, Taipei 106, Taiwan, Republic of China.No affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info available

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

21942211

Citation

Chuang, Wei-Ti, et al. "Excited-state Intramolecular Proton Transfer Molecules Bearing O-hydroxy Analogues of Green Fluorescent Protein Chromophore." The Journal of Organic Chemistry, vol. 76, no. 20, 2011, pp. 8189-202.
Chuang WT, Hsieh CC, Lai CH, et al. Excited-state intramolecular proton transfer molecules bearing o-hydroxy analogues of green fluorescent protein chromophore. J Org Chem. 2011;76(20):8189-202.
Chuang, W. T., Hsieh, C. C., Lai, C. H., Lai, C. H., Shih, C. W., Chen, K. Y., Hung, W. Y., Hsu, Y. H., & Chou, P. T. (2011). Excited-state intramolecular proton transfer molecules bearing o-hydroxy analogues of green fluorescent protein chromophore. The Journal of Organic Chemistry, 76(20), 8189-202. https://doi.org/10.1021/jo2012384
Chuang WT, et al. Excited-state Intramolecular Proton Transfer Molecules Bearing O-hydroxy Analogues of Green Fluorescent Protein Chromophore. J Org Chem. 2011 Oct 21;76(20):8189-202. PubMed PMID: 21942211.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Excited-state intramolecular proton transfer molecules bearing o-hydroxy analogues of green fluorescent protein chromophore. AU - Chuang,Wei-Ti, AU - Hsieh,Cheng-Chih, AU - Lai,Chin-Hung, AU - Lai,Cheng-Hsuan, AU - Shih,Chun-Wei, AU - Chen,Kew-Yu, AU - Hung,Wen-Yi, AU - Hsu,Yu-Hsiang, AU - Chou,Pi-Tai, Y1 - 2011/09/29/ PY - 2011/9/28/entrez PY - 2011/9/29/pubmed PY - 2012/2/9/medline SP - 8189 EP - 202 JF - The Journal of organic chemistry JO - J Org Chem VL - 76 IS - 20 N2 - o-Hydroxy analogues, 1a-g, of the green fluorescent protein chromophore have been synthesized. Their structures and electronic properties were investigated by X-ray single-crystal analyses, electrochemistry, and luminescence properties. In solid and nonpolar solvents 1a-g exist mainly as Z conformers that possess a seven-membered-ring hydrogen bond and undergo excited-state intramolecular proton transfer (ESIPT) reactions, resulting in a proton-transfer tautomer emission. Fluorescence upconversion dynamics have revealed a coherent type of ESIPT, followed by a fast vibrational/solvent relaxation (<1 ps) to a twisted (regarding exo-C(5)-C(4)-C(3) bonds) conformation, from which a fast population decay of a few to several tens of picoseconds was resolved in cyclohexane. Accordingly, the proton-transfer tautomer emission intensity is moderate (0.08 in 1e) to weak (∼10(-4) in 1a) in cyclohexane. The stronger intramolecular hydrogen bonding in 1g suppresses the rotation of the aryl-alkene bond, resulting in a high yield of tautomer emission (Φ(f) ≈ 0.2). In the solid state, due to the inhibition of exo-C(5)-C(4)-C(3) rotation, intense tautomer emission with a quantum yield of 0.1-0.9 was obtained for 1a-g. Depending on the electronic donor or acceptor strength of the substituent in either the HOMO or LUMO site, a broad tuning range of the emission from 560 (1g) to 670 nm (1a) has been achieved. SN - 1520-6904 UR - https://www.unboundmedicine.com/medline/citation/21942211/Excited_state_intramolecular_proton_transfer_molecules_bearing_o_hydroxy_analogues_of_green_fluorescent_protein_chromophore_ L2 - https://doi.org/10.1021/jo2012384 DB - PRIME DP - Unbound Medicine ER -