A Bistable Molecular Switch Driven by Photoinduced Hydrogen‐Atom Transfer

Lapiński, Leszek; Nowak, Maciej J.; Nowacki, Jacek; Rode, Michał F.; Sobolewski, Andrzej L.

doi:10.1002/cphc.200900190

Cited by 53 publications

(56 citation statements)

References 30 publications

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“…This property is termed molecular photochromism. [11][12][13][14][15][16][17] In recent decades, systems that exhibit the phenomenon of excited-state intramolecular proton transfer (ESIPT) have been of considerable applied interest as photostabilizers and sunscreens for the protection of organic polymers and biological tissues against damage that can be caused by the UV component of sunlight. [5] Over the years, most research effort in this field has been focused on two classes of intramolecular reactions related to photochromism.…”

Section: Introductionmentioning

confidence: 99%

“…[5] Over the years, most research effort in this field has been focused on two classes of intramolecular reactions related to photochromism. [11][12][23][24][25][26][27] A qualitative photophysical scheme for optically driven molecular switches based on the ESIPT phenomenon was proposed by us recently. [9 and 10]).…”

Section: Introductionmentioning

confidence: 99%

“…More recently, a new class of photochromic systems subjected to a light-induced intramolecular proton-transfer (PT) process has been invoked. [11][12][13][14][15][16][17] In recent decades, systems that exhibit the phenomenon of excited-state intramolecular proton transfer (ESIPT) have been of considerable applied interest as photostabilizers and sunscreens for the protection of organic polymers and biological tissues against damage that can be caused by the UV component of sunlight. [18][19][20][21] Of these systems, photochromic Schiff bases [22] represent a special group of ESIPT systems, for which depopulation routes of the excited molecule are particularly complex.…”

Section: Introductionmentioning

confidence: 99%

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Excited‐State Intramolecular Proton Transfer: Photoswitching in Salicylidene Methylamine Derivatives

et al. 2014

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The effect of chemical substitutions on the photophysical properties of the salicylidene methylamine molecule (SMA) (J. Jankowska, M. F. Rode, J. Sadlej, A. L. Sobolewski, ChemPhysChem, 2012, 13, 4287-4294) is studied with the aid of ab initio electronic structure methods. It is shown that combining π-electron-donating and π-electron-withdrawing substituents results in an electron-density push-and-pull effect on the energetic landscape of the ground and the lowest excited ππ* and nπ* singlet states of the system. The presented search for the most appropriate SMA derivatives with respect to their photoswitching functionality offers an efficient prescreening tool for finding chemical structures before real synthetic realization.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Excited‐State Intramolecular Proton Transfer: Photoswitching in Salicylidene Methylamine Derivatives

et al. 2014

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“…[23] Molecules exhibiting such processes are termed as molecular switches. Systems of this kind are of great research interest nowadays [23][24][25][26][27][28][29][30][31][32][33][34][35][36][37] because of their wide-range applications. Due to their small size, switches play a significant role in miniaturization demonstrating the importance for studying them.…”

Section: Introductionmentioning

confidence: 99%

Molecular switch properties of 7‐hydroxyquinoline compounds

Csehi

Halász

Vibók

2014

Int J of Quantum Chemistry

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The present study is concerned with the theoretical study of possible molecular switch systems. The 7-hydroxyquinoline-8-carboxamide molecule and its single-, double-, and triplesubstituted derivatives are investigated with the aim of revealing characteristic switch features. Molecular switches can be considered as composed of a frame and a crane component. According to a recent study, the 7-hydroxyquinoline doublering system constitutes the frame moiety, while a carboxamide group at position 8 plays the role of the crane part (Csehi et al., Phys. Chem. Chem. Phys. 2013, 15, 18048). The effect of single 2-,4-,6-methyl, double 2,4-, 2,6-diamino, and triple 2,4,6-triamino substitutions to the molecular frame has been investigated using high level ab initio techniques. As a possible reaction mechanism, excited state intramolecular hydrogen transfer mediated by the frame-crane torsion has been considered. At the terminal structures of this pathway, second-order approximate coupled-cluster (CC2) quality vertical excitation energies and oscillator strengths have been calculated for the three lowest-lying singlet electronic excited states of all the studied systems. Single point calculations at selected geometries of the reaction path were carried out at the CC2 level as well, while conical intersections (CIs) between the ground and first excited states near perpendicular twisted geometries were optimized using the complete active space self-consistent field method. To confirm the presence of CIs, nonadiabatic coupling terms have been derived and applying the topological line integral technique, the topological (or Berry) phase has been calculated surrounding the point of CI. The results of this work clearly demonstrate the fulfillment of several molecular switch properties by the investigated quinoline derivatives. An extensive comparison between the different compounds is presented as well.

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“…Molecular switches have potential applications in many areas and are thus an area of great research interest [15][16][17][18][19][20][21][22][23][24][25][26][27][28]. Due to their small size, switches play an important role in miniaturization [19] by permitting ultra-high density data storage on a molecular level.…”

Section: Introductionmentioning

confidence: 99%

Ab initio studies of two pyrimidine derivatives as possible photo-switch systems

et al. 2013

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Abstract:The six lowest lying electronic singlet states of 8-(pyrimidine-2-yl)quinolin-ol and 2-(4-nitropyrimidine-2-yl)ethenol have been studied theoretically using the complete active space self-consistent-field (CASSCF) and Møller-Plesset second-order perturbation theory (MP2) methods. Both molecules can be viewed as consisting of a frame and a crane component. As a possible mechanism for the excited-state relaxation process an intramolecular hydrogen transfer promoted by twisting around the covalent bond connecting the molecular frame and crane moieties has been considered. Based on this idea we have attempted to derive abstracted photochemical pathways for both systems. Geometry optimizations for the construction of hypothetical reaction coordinates have been performed at the MP2 level of theory while the CASSCF approach has been employed for the calculation of vertical excitation energies along the pathways. The results of the calculations along the specific twisting displacements investigated in this study do not support the notion of substantial twisting activity upon excitation of any of the five excited states at the planar terminal structures of the torsion coordinates of both molecules. However, the present analysis should be considered only as a first, preliminary step towards an understanding of the photochemistry of the two candidate compounds. For example, we have not performed any excited state geometry optimizations so far and the estimates of vertical excitation energies do not take dynamical electron correlation into account. Further work on this subject is in progress. 31.50.-x, 33.15.-e PACS (2008):

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A Bistable Molecular Switch Driven by Photoinduced Hydrogen‐Atom Transfer

Cited by 53 publications

References 30 publications

Excited‐State Intramolecular Proton Transfer: Photoswitching in Salicylidene Methylamine Derivatives

Excited‐State Intramolecular Proton Transfer: Photoswitching in Salicylidene Methylamine Derivatives

Molecular switch properties of 7‐hydroxyquinoline compounds

Ab initio studies of two pyrimidine derivatives as possible photo-switch systems

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