Ultrafast single and double proton transfer in photo-excited [2,2′-bipyridyl]-3,3′-diol

Zhang, H.; Meulen, P. van der; Glasbeek, M.

doi:10.1016/0009-2614(96)00213-8

Cited by 91 publications

(99 citation statements)

References 26 publications

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“…[8] This molecule had been carefully studied by Glasbeek and co-workers, [9][10][11][12][13] who carried out a series of time-resolved experiments in the sub-picosecond time range. From these studies it was concluded that the ESIDPT in BP(OH) 2 was a branched mechanism and consisted of: 1) a concerted reaction channel, where both protons exchange sites simultaneously and 2) a stepwise channel, where one proton transfers first and the other proton transfers upon completion of the first step.…”

Section: Introductionmentioning

confidence: 99%

A Comparative Study on the Photochemistry of Two Bipyridyl Derivatives: [2,2′‐Bipyridyl]‐3,3′‐diamine and [2,2′‐Bipyridyl]‐3,3′‐diol

et al. 2007

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The two isoelectronic bipyridyl derivatives, [2,2'-bipyridyl]-3,3'-diamine and [2,2'-bipyridyl]-3,3'-diol, are experimentally known to undergo very different excited-state double-proton-transfer processes, which result in fluorescence quantum yields that differ by four orders of magnitude. Herein, density functional theory (DFT), time-dependent DFT (TDDFT), and complete active space self-consistent field (CASSCF) calculations are used to study the double-proton-transfer processes in the ground and first singlet pi-->pi* excited state. The quantum-chemistry calculations indicate 1) the existence of only one energy minimum in the ground electronic state corresponding to reactants (thus avoiding the possibility of a fast fluorescent relaxation process from the photoproducts region), 2) an endoergic process of the complete double proton transfer, and 3) the presence of a conical intersection in the excited intermediate region of [2,2'-bipyridyl]-3,3'-diamine. These facts explain the very low fluorescence quantum yield in [2,2'-bipyridyl]-3,3'-diamine compared to [2,2'-bipyridyl]-3,3'-diol.

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Section: Introductionmentioning

confidence: 99%

A Comparative Study on the Photochemistry of Two Bipyridyl Derivatives: [2,2′‐Bipyridyl]‐3,3′‐diamine and [2,2′‐Bipyridyl]‐3,3′‐diol

et al. 2007

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“…[28] In recent years we have studied a series of isoA C H T U N G T R E N N U N G electronic molecules with [2,2'-bipyridyl]-3,3'-diol (hereafter referred www.chemeurj.org to as BP(OH) 2 ), one of the simplest molecules that is experimentally known to suffer a double proton transfer in the excited state. [29][30][31][32][33] In addition to studying the parent molecule, [34] we have also investigated the isoelectronic deriva- [35] and [2,2'-bipyridyl]-3-amin-3'ol (BP(OH)A C H T U N G T R E N N U N G (NH 2 )). [36] In spite of the similarities between the three molecular systems (the only change being the substitution of one or two hydroxy groups by amino ones), they show quite different photochemical behavior.…”

Section: Introductionmentioning

confidence: 99%

Bipyridyl Derivatives as Photomemory Devices: A Comparative Electronic‐Structure Study

Ortiz-Sánchez

Gelabert

Moreno

et al. 2010

Chemistry A European J

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The two isoelectronic bipyridyl derivatives [2,2'-bipyridyl]-3,3'-diamine (BP(NH(2))(2)) and [2,2'-bipyridyl]-3,3'-diol (BP(OH)(2)) are experimentally known to undergo very different excited-state double proton transfer processes that result in fluorescence quantum yields that differ by four orders of magnitude. Such differences have been theoretically explained in terms of topographical features in the potential energy surface and the likely presence of conical intersections. The hypothetical hybrid compound [2,2'-bipyridyl]-3-amin-3'-ol (BP(OH)(NH(2))) presents intermediate photochemical features of its "ancestors". In this report we analyze the photochemical properties of a whole family of "dark" (not fluorescent) states that can be accessed from each bipyridyl derivative upon irradiation of light of a given wavelength and their potential application as photomemory devices. In the light of our density functional theory (DFT), time-dependent DFT (TDDFT), and complete active space self-consistent field (CASSCF) calculations, BP(NH(2))(2) is the more likely candidate to become a photomemory device.

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“…Glasbeek and coworkers performed a series of femtochemistry experiments that led to the conclusion that ESIDPT in BP(OH) 2 is a branched mechanism where the concerted and stepwise processes are in competition. [28][29][30][31][32] Later on, the same research group reported on the isoelectronic species 2,2'-[bipyridyl]-3,3'-diamine [hereafter referred to as BP(NH 2 ) 2 ], finding remarkable differences with BP(OH) 2 , the more noticeable one being a large decrease (four orders of magnitude) of the fluorescence quantum yield. [33] We have recently performed a series of electronic calculations on both bipyridyl molecules which provides a theoretical basis for the experimentally observed differences between both compounds.…”

Section: Introductionmentioning

confidence: 97%

“…In fact, experimental results point to DK* as the final product of the ESIPT process in S 1 . [28][29][30][31][32] A high fluorescence yield (0.32) and a large Stokes shift of the fluorescence vs absorption band (510 and 340 nm, respectively) are additional proof that the photochemical reaction proceeds along the path: DE!DE*!DK*!DK! DE.…”

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confidence: 97%

Modulating the Photochemistry of Bipyridylic Compounds by Symmetric Substitutions

et al. 2010

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A quantum electronic study of the effect of substituents on (2,2'-bipyridyl)-3,3'-diol and (2,2'-bipyridyl)-3,3'-diamine is presented. A large difference in the photochemical behavior between the original and the substituted selected systems is expected. For the sake of simplicity, the study is restricted to the symmetrically bi-substituted compounds: fluorine, the more electronegative atom and thus a strong σ-acceptor but also a weak π-donor group, and NO(2), a strong π-acceptor substituent. Among the large set of compounds studied, two receive special attention: 5,5'-dinitro-(2,2'-bipyridyl)-3,3'-diamine and 6,6'-difluoro-(2,2'-bipyridyl)-3,3'-diol. While in the former case the nitro substitution transforms (2,2'-bipyridyl)-3,3'-diamine, previously suggested to behave as a photomemory material, into a simple fluorescent species, the latter substitution turns (2,2'-bipyridyl)-3,3'-diol into a fresh new candidate for a photomemory device.

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Ultrafast single and double proton transfer in photo-excited [2,2′-bipyridyl]-3,3′-diol

Cited by 91 publications

References 26 publications

A Comparative Study on the Photochemistry of Two Bipyridyl Derivatives: [2,2′‐Bipyridyl]‐3,3′‐diamine and [2,2′‐Bipyridyl]‐3,3′‐diol

A Comparative Study on the Photochemistry of Two Bipyridyl Derivatives: [2,2′‐Bipyridyl]‐3,3′‐diamine and [2,2′‐Bipyridyl]‐3,3′‐diol

Bipyridyl Derivatives as Photomemory Devices: A Comparative Electronic‐Structure Study

Modulating the Photochemistry of Bipyridylic Compounds by Symmetric Substitutions

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