Tuning the Redox Properties of Photochromic Diarylethenes by Introducing Electron‐Withdrawing Substituents

Berberich, Martin; Würthner, Frank

doi:10.1002/ajoc.201200179

Cited by 11 publications

(8 citation statements)

References 49 publications

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“…Thus, a strongly electron-deficient substituent such as pyridinium is necessary to shift the reduction potential to accessible values. However, not every electron-withdrawing group appears to be suited to induce cathodic cyclization [ 40 , 42 ].…”

Section: Resultsmentioning

confidence: 99%

Oxidative and reductive cyclization in stiff dithienylethenes

Kleinwächter¹,

Teichmann²,

Grubert³

et al. 2018

Beilstein J. Org. Chem.

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The electrochemical behavior of stiff dithienylethenes, undergoing double bond isomerization in addition to ring-closure, has been investigated. Electrochromism was observed in almost all cases, with the major pathway being the oxidatively induced cyclization of the open isomers. The influence of the ring size (to lock the reactive antiparallel conformation) as well as substituents (to modulate the redox potential) on the electrocyclization was examined. In the series of derivatives with 6-membered rings, both the E- and the Z-isomer convert to the closed isomer, whereas for the 7-membered rings no cyclization from the E-isomer was observed. For both stiff and normal dithienylethenes bearing benzonitrile substituents an additional and rare reductive electrocyclization was observed. The mechanism underlying both observed electrocyclization pathways has been elucidated.

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Section: Resultsmentioning

confidence: 99%

Oxidative and reductive cyclization in stiff dithienylethenes

Kleinwächter¹,

Teichmann²,

Grubert³

et al. 2018

Beilstein J. Org. Chem.

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“…The reduction potential has strongly related to the kind of the substituent and their position . It is reported that the reduction potential of organic molecules becomes higher when the electron withdrawing substituent is placed . The overall trend of the reduction potential that increase with the electron withdrawing group is confirmed for these metal complexes.…”

Section: Resultsmentioning

confidence: 55%

Prediction of the reduction potential of tris(2,2′-bipyridinyl)iron(III/II) derivatives

Park

Lee

2014

J. Comput. Chem.

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The reduction potentials of a tris(2,2'-bipyridinyl)iron (III/II) and iron(III/II) couples complexed with 2,2'-bipyridinyl derivatives in acetonitrile are predicted using density functional theory. The calculation protocol proposed by Kim et al. (Kim, J. Park, Y. S. Lee, J. Comput. Chem. 2013, 34, 2233) showing reliable performance for the reduction potential is used. The four kinds of the functional groups, a methoxy group, a methyl group, a chlorine atom, and a cyanide group, are substituted at the ligands to examine the electronic effect on the reduction potential. Electron donating/withdrawing effect is analyzed by comparing the reduction potential having different substituents at the same position. The influence of the geometrical strain on the reduction potential is investigated. The good correlation between the experimental results and the calculated results is obtained. Not only the general trend, but also the detailed phenomena are correctly reproduced. The maximum deviation from the experimental value is 0.083 V for the methyl substitution at the position 4. The mean absolute error for the seven couples is 0.047 V. The difference of the reduction potential between the chlorine atom substituted at the positions 4 and 5, 0.1 V, is well described. The difference between the CN and the Cl substitution of 0.318 and 0.228 V for the position 4 and 5 is correctly obtained as 0.325 and 0.213 V, respectively. The simple linear relation between the lowest unoccupied molecular orbital (LUMO) energy of the Fe(III) complexes in solution and the calculated reduction potentials is obtained with the R(2) of 0.977.

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“…The organic phase was extracted with ether (3 × 50 mL), and the organic layers were collected, washed with brine (2 × 50 mL), dried over MgSO 4 , filtered, and evaporated under vacuum. The resulting mixture was purified by flash column chromatography (100% hexane) to give 4 as a yellow solid (3.62 g, 62%) as mixture of parallel (p) and antiparallel (ap) isomers in a ratio of 36:64; mp 153–154 °C [lit . 154–156 °C].…”

Section: Methodsmentioning

confidence: 99%

“…The resulting mixture was purified by flash column chromatography (100% hexane) to give 4 as a yellow solid (3.62 g, 62%) as mixture of parallel (p) and antiparallel (ap) isomers in a ratio of 36…”

Section: 3'-(perfluorocyclopent-1-ene-12-diyl)bis(2-methylbenzothiophene) (4)mentioning

confidence: 99%

Fabrication of Robust Spatially Resolved Photochromic Patterns on Cellulose Papers by Covalent Printing for Anticounterfeiting Applications

Bretel

Grognec

Jacquemin

et al. 2019

ACS Appl. Polym. Mater.

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Despite its millennial age, cellulose paper remains the preferred material for domestic and professional printings, covering applications from simple office paperwork to fiducial solutions such as bills, passports, and head letters. The creation of robust photochromic patterns on cellulose papers for anti-counterfeiting applications is an important and still partially unaddressed challenge. In this contribution, we report the covalent printing of dibenzothienylethenes as photochromic compounds through a spatially-controlled light mediated thiol-X ligations. Photophysical and theoretical studies provide evidences for a reversible photochromism behavior, not affected significantly by the polar environment of the cellulose matrix, and demonstrates a high fatigue resistance over 18 successive write-erase cycles. The strong coloration-discoloration switch can be easily followed by a direct nakedeye readout.

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Tuning the Redox Properties of Photochromic Diarylethenes by Introducing Electron‐Withdrawing Substituents

Cited by 11 publications

References 49 publications

Oxidative and reductive cyclization in stiff dithienylethenes

Oxidative and reductive cyclization in stiff dithienylethenes

Prediction of the reduction potential of tris(2,2′-bipyridinyl)iron(III/II) derivatives

Fabrication of Robust Spatially Resolved Photochromic Patterns on Cellulose Papers by Covalent Printing for Anticounterfeiting Applications

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