A Photocontrolled Molecular Switch Regulates Paralysis in a Living Organism

Al-Atar, Usama; Fernandes, Rylan; Johnsen, Bob; Baillie, David L.; Branda, Neil R.

doi:10.1021/ja903070u

Cited by 152 publications

(96 citation statements)

References 14 publications

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“…The use of organic molecules for the future realization of digital processors and storage media at the miniaturized level is at present a hot topic in applied science. [24][25][26][27] A molecule that exhibits the simple behavior shown in Figure 1b could be a good candidate for a molecular photomemory device if the photochromic species is stable enough. To accomplish this, additional stabilization of this isomer should be possible, for example, through the formation of a new hydrogen bond.…”

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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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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“…Among the structurally diverse range of organic photochromes including fulgides, spiropyrans, overcrowded alkenes, dihydroindolizines, catenanes, etc., the synthetic versatility, thermal stability, and combination of electro-and photosensitive properties place diarylethenes as a key structural unit. 1,2 The systematic study of their spectral, physical, and electronic properties and the design and synthesis of new diarylethene molecules 1,2 has led to the widespread application of these switches in molecular electronics, [3][4][5][6] molecular magnetism, 7 fine chemical synthesis, 8 cell biology, 9 and spectroscopy. 1 These studies over the past decade have led to the design and fabrication of molecular devices, based on diarylethenes, in which the electrical conductivity in nanojunctions can be controlled.…”

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confidence: 99%

“…1,8,12,13 Finally, the successful use of diarylethenes in labeling living cells shows a possibility for future application in novel drug design and drug discovery techniques. 9 The application of diarylethenes in such a wide range of areas is as a result of the different electronic properties of two thermally stable isomeric forms: an open-ring structure and a closed-ring structure each of which has a distinct geometry, UV/vis absorption spectrum and redox properties. 1,14,15 The switching of diarylethenes occurs through a ring cyclization (open to closed form) or ring cycloreversion (closed to open form) reaction.…”

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confidence: 99%

Electrochemical and Photochemical Cyclization and Cycloreversion of Diarylethenes and Diarylethene-Capped Sexithiophene Wires

et al. 2011

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A combined theoretical and experimental study was performed on diarylethenes and diarylethene-capped sexithiophenes aiming at an improved understanding of the electrochemical and photochemical ring-opening and ring-closing mechanisms. Theoretical calculations, based on DFT and TDDFT, suggested that the spatial distribution and the occupancy of the frontier orbitals determine and control the diarylethenes’ ring-opening and ring-closing upon photoirradiation and electrochemical oxidation. Optimized geometries, potential energy surfaces, and activation energies between the open-ring and closed-ring forms were calculated for diarylethenes in the neutral ground state, excited states, and mono- and dicationic states. Analysis of the frontier orbitals was employed to understand the cyclization and cycloreversion of diarylethenes and to predict and explain the switching properties of diarylethene-capped sexithiophene molecular wires. The TDDFT data were verified with experimentally measured UV/vis spectra. The DFT calculations estimated open-shell ground states of diarylethene-capped sexithiophene dications, which were verified with EPR spectroscopy, and the broadening of the peaks in the EPR spectra were explained with the calculated singlet−triplet splitting. The good agreement of experiment and theory allows for the understanding of switching behavior of diarylethenes in solutions, in metal break junctions, in monolayers on metal surfaces, and as a part of complex organic molecular wires.

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“…[14][15][16] In most cases, pyridine was introduced to the diarylethenes as a peripheral substituent. [17][18][19] In previous works, we reported some diarylethenes with a pyridine moiety directly linked at the central cyclopentene moiety and elucidated their specific photoactive characteristics. 20 The results obtained have contributed to a broad understanding of the photochromism of pyridine-containing diarylethene derivatives.…”

Section: Introductionmentioning

confidence: 99%

Effects of the Peripheral Heteroaryl Substituents on the Photochromism of New Pyridine-Containing Diarylethenes

Liao

Xue

Zheng

et al. 2016

Journal of the Brazilian Chemical Society

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Three new unsymmetrical pyridine-containing diarylethenes with a variable peripheral heteroaryl unit were synthesized and their structures were determined by single-crystal X-ray diffraction analysis. The substituent effects of variable heteroaryl groups on the photochromic and fluorescence properties were systematically discussed. Thienyl and thiazyl could effectively enhance the cyclization quantum yields and photoconversion ratios in the photostationary state, as compared to the phenyl group. However, they had no obvious effect on the fluorescence behaviors. Moreover, X-ray structural analysis revealed that the N … S heteroatom-contact interactions resulted in a higher cyclization quantum yield, which may be ascribed to the effective stabilizing ability on the photoreactive formations in diarylethenes with a thienyl/thiazyl unit.

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A Photocontrolled Molecular Switch Regulates Paralysis in a Living Organism

Cited by 152 publications

References 14 publications

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

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

Electrochemical and Photochemical Cyclization and Cycloreversion of Diarylethenes and Diarylethene-Capped Sexithiophene Wires

Effects of the Peripheral Heteroaryl Substituents on the Photochromism of New Pyridine-Containing Diarylethenes

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