Theoretical Study on the Excited-State Intramolecular Proton Transfer in the Aromatic Schiff Base Salicylidene Methylamine:  an Electronic Structure and Quantum Dynamical Approach

Ortiz-Sánchez, Juan Manuel; Gelabert, Ricard; Moreno, Miquel; Lluch, José M.

doi:10.1021/jp0604600

Cited by 58 publications

(48 citation statements)

References 44 publications

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“…[57] As we stated in a previous report, [58] the B3LYP functionals used in the Gaussian 03 and Turbomole packages differ very little in the relative stability of the calculated points, which implies a very minor effect on our results. This small difference comes from the use of a different form of the local correlation functional: the Gaussian 03 package uses the VWNA C H T U N G T R E N N U N G (III) local correlation functional, whereas Turbomole uses VWN(V).…”

Section: Methodsmentioning

confidence: 85%

Study of the Photochemical Properties and Conical Intersections of [2,2′‐Bipyridyl]‐3‐amine‐3′‐ol

et al. 2008

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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. In a previous study, these differences were explained from a theoretical point of view, because of topographical features in the potential energy surface and the presence of conical intersections (CIs). Here, we analyze the photochemical properties of a new molecule, [2,2'-bipyridyl]-3-amine-3'-ol [BP(OH)(NH(2))], which is, in fact, a hybrid of the former two. Our density functional theory (DFT), time-dependent DFT (TDDFT), and complete active space self-consistent field (CASSCF) calculations indicate that the double-proton-transfer process in the ground and first singlet pi-->pi* excited state in BP(OH)(NH(2)) presents features that are between those of their "parents". The presence of two CIs and the role they may play in the actual photochemistry of BP(OH)(NH(2)) and other bipyridyl derivatives are also discussed.

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Section: Methodsmentioning

confidence: 85%

Study of the Photochemical Properties and Conical Intersections of [2,2′‐Bipyridyl]‐3‐amine‐3′‐ol

et al. 2008

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“…[56] As we stated in a previous paper, [57] the B3LYP functionals used in the Gaussian 03 and Turbomole packages differ very little in the relative stability of the calculated points, which implies a very small effect on our results. This small difference is a result of the use of a different form of the local correlation functional: The Gaussian 03 package uses the VWNA C H T U N G T R E N N U N G (III) local correlation functional, whereas Turbomole uses VWN(V).…”

Section: Computational Detailsmentioning

confidence: 90%

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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“…TDDFT has been succesfully used to study other ESIPT systems. [8,[25][26][27] The three-parameter hybrid functional of Becke with the correlation functional of Lee, Yang and Parr (B3LYP) [28,29] has been chosen. The TURBOMOLE program (Version 5.4), [30,31] which implements analytical gradients at the TDDFT level, has been used to perform the TDDFT calculations.…”

Section: Methodsmentioning

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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Theoretical Study on the Excited-State Intramolecular Proton Transfer in the Aromatic Schiff Base Salicylidene Methylamine: an Electronic Structure and Quantum Dynamical Approach

Cited by 58 publications

References 44 publications

Study of the Photochemical Properties and Conical Intersections of [2,2′‐Bipyridyl]‐3‐amine‐3′‐ol

Study of the Photochemical Properties and Conical Intersections of [2,2′‐Bipyridyl]‐3‐amine‐3′‐ol

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

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

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