2009
DOI: 10.1002/chem.200802428
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Abstract: The rates of double hydrogen transfer in the ground and excited electronic states have been measured for porphycene and its derivatives by using a new method based on pump-probe polarization spectroscopy. Changing the strength of two intramolecular hydrogen bonds by altering the NHN distance leads to differences in the tautomerization rate exceeding three orders of magnitude. The reaction is considerably slower in the lowest electronically excited state. A correlation was found between the tautomerization rate… Show more

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Cited by 62 publications
(122 citation statements)
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“…[20] We have recently developed a technique, based on polarized femtosecond pump-probe spectroscopy, which makes it possible to determine the rate constant of tautomerization in a condensed, rigid environment. [21,22] The rate constants for both ground and lowest excited electronic states have been determined for the parent porphycene and several derivatives. Varying the NH···N distance, and in consequence, the HB strength by using alkyl substituents resulted in a huge variation in the tautomerization rate, from values larger than 10 13 s À1 for derivatives with the strongest HB (meso-tetrasubstituted porphycenes) to less than 10 10 s À1 for the derivatives with the weakest HB (b,b'-octaalkyl derivatives).…”
Section: Introductionmentioning
confidence: 99%
“…[20] We have recently developed a technique, based on polarized femtosecond pump-probe spectroscopy, which makes it possible to determine the rate constant of tautomerization in a condensed, rigid environment. [21,22] The rate constants for both ground and lowest excited electronic states have been determined for the parent porphycene and several derivatives. Varying the NH···N distance, and in consequence, the HB strength by using alkyl substituents resulted in a huge variation in the tautomerization rate, from values larger than 10 13 s À1 for derivatives with the strongest HB (meso-tetrasubstituted porphycenes) to less than 10 10 s À1 for the derivatives with the weakest HB (b,b'-octaalkyl derivatives).…”
Section: Introductionmentioning
confidence: 99%
“…22 The corresponding rate for porphyrin is many orders of magnitude lower (2600 s À1 at 267 K). 8 Also the mechanisms of tautomerization are different.…”
Section: Introductionmentioning
confidence: 99%
“…6). While the plots for 0fs 2 and −1600fs 2 are clearly nonlinear indicating a saturated absorption regime, data for 1200fs 2 can be satisfactorily fitted with a straight line. This result serves as an additional confirmation that despite high energy density in the illuminated region of the sample, resonant interactions with positively chirped pulses are primarily of non-saturated (single-photon) nature.…”
Section: Control Of Electronic Populations In Porphycene With Chirpedmentioning
confidence: 88%
“…1), attracts considerable interest of researchers primarily due to intramolecular double hydrogen transfer occurring near its internally-positioned nitrogens [1]. This process has been successfully studied with pump-probe ultrafast techniques, yielding information on both ground-and excited-state hydrogen transfer rates in a variety of porphycene derivatives [2,3]. In this work, we focus on population control in porphycene and show that the transient absorption signal related to populations in both ground and excited state can be modified by more than 100% by varying only the linear chirp of a high intensity pump pulse while keeping both its energy and spectrum constant.…”
mentioning
confidence: 99%
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