Abstract
Fluorescence quenching behaviors of four known excited-state intramolecular proton transfer (ESIPT) molecules have been studied by semiempirical and ab initio calculations. The ESIPT compounds studied in this work are assorted into two sets depending on the N-containing ring structure (5- and 6-membered rings). It has been found that twisted intramolecular charge transfer (TICT) process in the excited keto state (K*) after ESIPT, one of the possible quenching pathways of ESIPT fluorescence, is significantly influenced by the geometrical properties of intramolecular hydrogen (H) bond associated with the N-containing ring structure. The compounds with 5-membered ring have efficient ESIPT emission with large barrier to fluorescence-quenching TICT state, due to appropriate stabilization of planar K* through intramolecular H bond. For the compounds with 6-membered ring, however, ESIPT emission is completely quenched due to significantly lowered barrier resulting from too short H-bond length. The effect of intramolecular H bond on the TICT reaction potential has been discussed in detail from the viewpoints of molecular structure and torsional motion, with the help of elaborate model compound studies.
| Original language | English |
|---|---|
| Pages (from-to) | 19-24 |
| Number of pages | 6 |
| Journal | Journal of Photochemistry and Photobiology A: Chemistry |
| Volume | 191 |
| Issue number | 1 |
| DOIs | |
| Publication status | Published - 2007 Sep 7 |
| Externally published | Yes |
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Keywords
- Excited-state intramolecular proton transfer (ESIPT)
- Fluorescence quenching
- Intramolecular hydrogen bond
- Semiempirical and ab initio calculations
- Twisted intramolecular charge transfer (TICT)
ASJC Scopus subject areas
- Chemistry(all)
- Chemical Engineering(all)
- Physics and Astronomy(all)
Cite this
Torsion-induced fluorescence quenching in excited-state intramolecular proton transfer (ESIPT) dyes. / Kim, Sehoon; Seo, Jangwon; Park, Soo Young.
In: Journal of Photochemistry and Photobiology A: Chemistry, Vol. 191, No. 1, 07.09.2007, p. 19-24.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Torsion-induced fluorescence quenching in excited-state intramolecular proton transfer (ESIPT) dyes
AU - Kim, Sehoon
AU - Seo, Jangwon
AU - Park, Soo Young
PY - 2007/9/7
Y1 - 2007/9/7
N2 - Fluorescence quenching behaviors of four known excited-state intramolecular proton transfer (ESIPT) molecules have been studied by semiempirical and ab initio calculations. The ESIPT compounds studied in this work are assorted into two sets depending on the N-containing ring structure (5- and 6-membered rings). It has been found that twisted intramolecular charge transfer (TICT) process in the excited keto state (K*) after ESIPT, one of the possible quenching pathways of ESIPT fluorescence, is significantly influenced by the geometrical properties of intramolecular hydrogen (H) bond associated with the N-containing ring structure. The compounds with 5-membered ring have efficient ESIPT emission with large barrier to fluorescence-quenching TICT state, due to appropriate stabilization of planar K* through intramolecular H bond. For the compounds with 6-membered ring, however, ESIPT emission is completely quenched due to significantly lowered barrier resulting from too short H-bond length. The effect of intramolecular H bond on the TICT reaction potential has been discussed in detail from the viewpoints of molecular structure and torsional motion, with the help of elaborate model compound studies.
AB - Fluorescence quenching behaviors of four known excited-state intramolecular proton transfer (ESIPT) molecules have been studied by semiempirical and ab initio calculations. The ESIPT compounds studied in this work are assorted into two sets depending on the N-containing ring structure (5- and 6-membered rings). It has been found that twisted intramolecular charge transfer (TICT) process in the excited keto state (K*) after ESIPT, one of the possible quenching pathways of ESIPT fluorescence, is significantly influenced by the geometrical properties of intramolecular hydrogen (H) bond associated with the N-containing ring structure. The compounds with 5-membered ring have efficient ESIPT emission with large barrier to fluorescence-quenching TICT state, due to appropriate stabilization of planar K* through intramolecular H bond. For the compounds with 6-membered ring, however, ESIPT emission is completely quenched due to significantly lowered barrier resulting from too short H-bond length. The effect of intramolecular H bond on the TICT reaction potential has been discussed in detail from the viewpoints of molecular structure and torsional motion, with the help of elaborate model compound studies.
KW - Excited-state intramolecular proton transfer (ESIPT)
KW - Fluorescence quenching
KW - Intramolecular hydrogen bond
KW - Semiempirical and ab initio calculations
KW - Twisted intramolecular charge transfer (TICT)
UR - http://www.scopus.com/inward/record.url?scp=34547667161&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=34547667161&partnerID=8YFLogxK
U2 - 10.1016/j.jphotochem.2007.03.026
DO - 10.1016/j.jphotochem.2007.03.026
M3 - Article
AN - SCOPUS:34547667161
VL - 191
SP - 19
EP - 24
JO - Journal of Photochemistry and Photobiology A: Chemistry
JF - Journal of Photochemistry and Photobiology A: Chemistry
SN - 1010-6030
IS - 1
ER -