Anomalous cage effect in the excited state dynamics of catechol in the 1 18 C 6-catecol host-guest complex 2 3

1 18C6-catecol host-guest complex 2 3 Fumiya Morishima, Ryoji Kusaka, Yoshiya Inokuchi, Takeharu Haino and Takayuki Ebata* 4 Department of Chemistry, Graduate School of Science, 5 Hiroshima University, Higashi-Hiroshima 739-8526, Japan 6 7 8 Abstract 9 We present the structure of 18C6-catechol host-guest complex and the effect of the 10 complexation on the S1 dynamics of catechol studied under a supersonically cooled gas phase 11 condition and in cyclohexane solution. In the gas phase bare catechol, two adjacent OH groups 12 have an intramolecular hydrogen-bonded structure. On the other hand, in the 18C6-catechol (1:1) 13 complex both of the catechol OH groups are hydrogen-bonded to the oxygen atoms of 18C6. This 14 complex formation greatly changes the character of the S1 state of catechol. That is, the S1 lifetime of 15 bare catechol is reported to be 7 ps, while the 18C6-catechol complex was obtained to be 10.3 ns. 16 This anomalous S1 lifetime elongation of catechol upon the complexation is attributed to a large 17 energy gap between the S1 (ππ*) and S2 states by the switching from the intramolecular 18 hydrogen-bond to the intermolecular hydrogen-bond in the host-guest complex. The formation of 19 the18C6-catechol complex formation was also confirmed in cyclohexane solution, and an anomalous 20 increase of fluorescence quantum yield of catechol was also observed. From the concentration 21 dependence of the fluorescence intensity, it was confirmed that 18C6 and catechol also form (1:1) 22 host-guest complex in bulk system. An equilibrium constant for 23 the18C6 + catechol ⇄ 18C6⋯ catechol reaction was obtained. It is suggested that that 18C6 can 24 act as a sensor of detecting catechol. 25

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