Molecular Seesaw: How Increased Hydrogen Bonding Can Hinder Excited-State Proton Transfer

被引:13
|
作者
Welsch, Ralph [1 ]
Driscoll, Eric [2 ]
Dawlaty, Jahan M. [2 ]
Miller, Thomas F., III [1 ]
机构
[1] CALTECH, Div Chem & Chem Engn, 1200 East Calif Blvd, Pasadena, CA 91125 USA
[2] Univ Southern Calif, Dept Chem, Los Angeles, CA 90089 USA
来源
JOURNAL OF PHYSICAL CHEMISTRY LETTERS | 2016年 / 7卷 / 18期
基金
美国国家科学基金会;
关键词
GAUSSIAN-BASIS SETS; ATOMS LI; DYNAMICS; ELECTRON; DENSITY; 1,3-BIS(2-PYRIDYLIMINO)-4,7-DIHYDROXYISOINDOLE; THERMOCHEMISTRY; MECHANISM; EXCHANGE; KR;
D O I
10.1021/acs.jpclett.6b01391
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
A previously unexplained effect in the relative rate of excited-state intramolecular proton transfer (ESIPT) in related indole derivatives is investigated using both theory and experiment. Ultrafast spectroscopy [J. Phys. Chem. A, 2015, 119, 5618-5625] found that although the diol 1,3-bis(2-pyridylimino)-4,7-dihydroxyisoindole exhibits two equivalent intramolecular hydrogen bonds, the ESIPT rate associated with tautomerization of either hydrogen bond is a factor of 2 slower than that of the single intramolecular hydrogen bond in the ethoxy-ol 1,3-bis(2-pyridylimino)-4-ethoxy-7-hydroxyisoindole. Excited-state electronic structure calculations suggest a resolution to this puzzle by revealing a seesaw effect in which the two hydrogen bonds of the diol are both longer than the single hydrogen bond in the ethoxy-ol. Semiclassical rate theory recovers the previously unexplained trends and leads to clear predictions regarding the relative H/D kinetic isotope effect (KIE) for ESIPT in the two systems. The theoretical KIE predictions are tested using ultrafast spectroscopy, confirming the seesaw effect.
引用
收藏
页码:3616 / 3620
页数:5
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