Influence of local microenvironment on the double hydrogen transfer in porphycene

Kasprzycki, Piotr; Kopycki, Przemysław; Listkowski, Arkadiusz; Gorski, Aleksander; Radzewicz, Czesław; Birch, David J. S.; Waluk, Jacek; Fita, Piotr

doi:10.1039/d0cp02687e

Cited by 4 publications

(3 citation statements)

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“…On the other hand, experiments carried out for polymer samples containing porphycene revealed at low temperatures the presence of two populations; in the first one, tautomerization was occurring on the subnanosecond time scale, whereas in the other it was too slow to be detected by nanosecond techniques. 29 In poly(methyl methacrylate) (PMMA), the fraction of hydrogen-transferring molecules was found to obey an Arrhenius-like equation, with the activation energy of 68 ± 2 cm –1 . This value coincides with 70 cm –1 , a low-frequency mode of PMMA.…”

Section: Environmental Effectsmentioning

confidence: 99%

Nuclear Quantum Effects in Proton or Hydrogen Transfer

Waluk

2024

J. Phys. Chem. Lett.

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Proton or hydrogen transfers, basic chemical reactions, proceed either by thermally activated barrier crossing or via tunneling. Studies of molecules undergoing single or double proton or hydrogen transfer in the ground or excited electronic state reveal that tunneling can dominate under conditions usually considered to favor the thermal process. Moreover, the tunneling probability strongly varies for excitation of certain vibrational modes, which changes the effective barrier and/or proton transfer distance. When the reaction is fast compared to vibrational relaxation, the mode selectivity can still be maintained for molecules in solutions at 293 K. These observations point to dangers of relating the calculated minimum energy paths and the associated barriers to the experimentally obtained activation energies. The multidimensional character of the reaction coordinate is obvious; it can dramatically change for slowly and rapidly relaxing environments. We postulate that the hydrogen bond definition should be extended by specifically including the role of molecular vibrations.

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Section: Environmental Effectsmentioning

confidence: 99%

Nuclear Quantum Effects in Proton or Hydrogen Transfer

Waluk

2024

J. Phys. Chem. Lett.

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“…[1][2][3][4][5][6][7][8][9][10] Noncovalent interactions have been utilized in the development of functional materials, [11][12][13] for tailoring crystallization, [14][15][16] or the study of host-guest interactions. [17][18][19] Reliably identifying noncovalent interactions is crucial in the understanding and development of novel functional materials. This article studies the noncovalent interactions in the 1:1 adduct of 4,4'-bipyridinium squarate (BIPY:SQA) as a function of temperature by diffraction methods.…”

Section: Introductionmentioning

confidence: 99%

Noncovalent bonding assessment by pair distribution function

et al. 2023

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“…Under such conditions, tautomerization in solution is very fast (femtoand picoseconds); 13 moreover, it is governed by tunneling, both ''deep'' (occurring from the vibrational ground state) and thermally activated after excitation of specific vibrational modes. 14 Tautomerization in porphycenes has been studied in various experimental regimes: ensemble studies in condensed phases, [13][14][15][16][17][18][19][20][21][22][23][24] investigations of ultracold molecules isolated in supersonic jets 25,26 or helium nanodroplets, 27 and, finally, single molecule techniques involving fluorescence, [28][29][30][31] Raman, 32,33 and scanning probe microscopy. [34][35][36][37][38][39][40] It has been demonstrated that photophysics of porphycenes and their tautomeric properties are strongly related.…”

Section: Introductionmentioning

confidence: 99%