An ab Initio MO Study of the Photochromic Reaction of Dithienylethenes

Guillaumont, Dominique; Kobayashi, Takao; Kanda, Katsuya; Miyasaka, Hiroshi; Uchida, Kôji; Kobatake, Seiya; Shibata, Katsunori M.; Nakamura, Shinichiro; Irie, Masahiro

doi:10.1021/jp021060p

Cited by 119 publications

(169 citation statements)

References 23 publications

(48 reference statements)

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“…Due to the high computational cost of the excited state optimization, the PES of the firstexcited state and second-excited state are calculated as vertical excitations for the ground state geometries. Calculations of the first-excited state PES of diarylethenes were reported in the literature with CASSCF, 17,27 TDDFT, 20 and by changing the occupation of the frontier orbitals by promoting an electron from HOMO to LUMO. 47 Despite the conceptional differences in the level of theory and degree of approximation, the calculated excited-state PESs are qualitatively similar.…”

Section: Resultsmentioning

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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Section: Resultsmentioning

confidence: 99%

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

et al. 2011

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“…Stepwise multiphoton processes in dithienylethene were studied in Ref. [178] The RES of several lowest singlet excited states were calculated at CAS(10,10)/6-31G and CAS(12,14)/6-31G theory levels. In all three of the excited states reported, the potential surfaces had a barrier to cycloreversion, located between the closed ring conformation and the pericyclic minimum.…”

Section: Benchmark Study Of Dithienylethenementioning

confidence: 99%

Theory and computations of two-photon absorbing photochromic chromophores

Masunov

Михайлов

2010

Eur. J. Chem.

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KEYWORDSExponential growth in information technology generates ever increasing amounts of data, making recording density of the storage media crucially important. Two-photon absorption was proposed as a basis for high-density multi-layer technology for optical memory and logic devices. This technology suggests to use polymers, doped with photochromic compounds that undergo a reversible photoinduced isomerization, or photoswitching. In this review we consider recent theoretical works and benchmarking studies of the DFT-based methods, capable to predict two-photon absorption (2PA) and photochemical activity, Next we review the applications of these methods to design a prototype molecule that combines the photonmode recording property of photochromic compounds with large 2PA cross-section. We conclude that a posteriori Tamm-Dancoff approximation to the second order CEO approach in Density Functional Theory is the powerful tool for both quantitative predictions and qualitative understanding of the excited state processes in photophysics and photochemistry. We also emphasize general principles for the rational design of a two-photon operated photoswitch.TDDFT Organic photochemistry Photocyclization Photoinduced reactions Two-photon absorption State-to-state transition dipoles

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“…The excited state PES features a local minimum with a geometry similar to that of the ground state closed isomer, and another local minimum with an inter-reactive-carbon bond length similar to that of the ground state transition state, but with a geometry similar to that of the ground state open isomer. 42 A conical intersection (CI) in close proximity to the latter minimum is proposed as the main pathway for both cyclization and cycloreversion reactions. 44,45 Due to their extended hydrocarbon structure diheteroarylethenes are known to be fairly insoluble in water and exhibit low fluorescence quantum yields and very poor photoconversion characteristics.…”

Section: Resultsmentioning

confidence: 99%

Photoswitchable fluorescent diheteroarylethenes: substituent effects on photochromic and solvatochromic properties

Gillanders

Giordano

Dı́az

et al. 2014

Photochem Photobiol Sci

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Photoswitchable fluorescent diheteroarylethenes are promising candidates for applications in superresolution molecular localization fluorescence microscopy thanks to their high quantum yields and fatigue-resistant photoswitching characteristics. We have studied the effect of varying substituents on the photophysical properties of six sulfone derivatives of diheteroarylethenes, which display fluorescence in one (closed form) of two thermally stable photochromic states. Electron-donating substituents displace the absorption and emission spectra towards the red without substantially affecting the fluorescence quantum yields. Furthermore, ethoxybromo, a very electron-donating substituent, stabilizes the excited state of the closed isomer to the extent of almost entirely inhibiting its cycloreversion. Multi-parameter Hammett correlations indicate a relationship between the emission maxima and electron-donating character, providing a useful tool in the design of future photochromic molecules. Most of the synthesized compounds exhibit small bathochromic shifts and shorter fluorescence lifetimes with an increase in solvent polarity. However, the ethoxybromo-substituted fluorescent photochrome is unique in its strong solvatochromic behaviour, constituting a photoactivatable ( photochromic), fluorescent and highly solvatochromic small organic compound. The Catalán formalism identified solvent dipolarity as the principal basis of the solvatochromism, reflecting the highly polarized nature of this molecule.

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An ab Initio MO Study of the Photochromic Reaction of Dithienylethenes

Cited by 119 publications

References 23 publications

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

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

Theory and computations of two-photon absorbing photochromic chromophores

Photoswitchable fluorescent diheteroarylethenes: substituent effects on photochromic and solvatochromic properties

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