Electrochemical Switching of Conductance with Diarylethene-Based Redox-Active Polymers

Logtenberg, Hella; Velde, Jasper H. M. van der; Mendoza, Paula de; Areephong, Jetsuda; Hjelm, Johan; Feringa, Ben L.; Browne, Wesley R.

doi:10.1021/jp307892s

Cited by 39 publications

(31 citation statements)

References 57 publications

(84 reference statements)

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“…Spectroscopic comparison with model compound 2 ( Scheme ), for which the open state forms H‐aggregates in solution at below 200 K, indicated that the extent of H‐type interactions in the polymer film was substantial and hence rapid excited state deactivation due to Davydov splitting precluded both fluorescence and photochemical switching . The introduction of a phenyl spacer unit between the dithienylethene and the dithiophene units restored the switching functionality of the dithienylethene unit in a polymer film, however, the quantum yield for photochemical switching was still lower than that observed in solution . The use of a methoxystyryl unit in place of the bithiophene unit also allows for electropolymerization with retention of the photo‐ and electrochemical switching properties of the dithienylethene unit, however, this is achieved at the cost of film thickness and poor film stability under UV irradiation .…”

Section: Methodsmentioning

confidence: 99%

Solvation Dependent Redox‐Gated Fluorescence Emission in a Diarylethene‐Based Sexithiophene Polymer Film

Kortekaas

Browne

2016

Advanced Optical Materials

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COMMUNICATION1o underwent oxidative polymerization readily to form thick conducting fi lms of a redox polymer (poly-1o ), whereas in its closed form, 1c , polymerization was not observed upon oxidation, ascribed to the extended π-conjugation in 1c and the coupling of the "radicals" formed upon one-electron oxidation of each half of the dithienyl ethene. Hence, the system provided for photochemical on/off switching of the polymerization of 1 . [ 18 ] Although dithienylethene photochromic switches readily undergo thermal cyclization and cycloreversion upon one-electron [ 19 ] or two-electron [ 20 ] oxidation (depending on the precise structure of the diarylethene), in the case of 1 the rate of electrochemical ring closing was suffi ciently low to allow for C C coupling at the terminal thiophene carbons to be competitive and for polymer fi lm formation to occur. The polymer fi lms formed, however, were found to be inert to both photo-and electrochemical switching and instead the spectroscopic and electrochemical properties of poly-1 appeared to be essentially those of an alkene bridged poly-sexithiophene polymer. [ 21 ] Spectroscopic comparison with model compound 2 [ 22 ] ( Scheme 2 ), for which the open state forms H-aggregates in solution at below 200 K, indicated that the extent of H-type interactions [ 23 ] in the polymer fi lm was substantial and hence rapid excited state deactivation due to Davydov splitting precluded both fl uorescence and photochemical switching. [ 24 ] The introduction of a phenyl spacer unit between the dithienylethene and the dithiophene units restored the switching functionality of the dithienylethene unit in a polymer fi lm, however, the quantum yield for photochemical switching was still lower than that observed in solution. [ 25 ] The use of a methoxystyryl unit in place of the bithiophene unit also allows for electropolymerization with retention of the photo-and electrochemical switching properties of the dithienylethene unit, however, this is achieved at the cost of fi lm thickness and poor fi lm stability under UV irradiation. [ 26 ] Recently, we demonstrated an alternative approach toward the preparation of photochemically switchable redox-polymers in which the functional unit (a bisspiropyran) was formed concomitant with polymerization of the monomer units. This approach provides polymer fi lms in which the properties of the switching unit observed in solution are retained fully in the polymer. [ 27 ] With these later approaches the photochromic functionality of dithienylethene switching unit is retained, however, the opportunity to modulate the intense fl uorescence of the sexithiophene unit by dual redox and photochemical control is lost. Although fi lms of poly-1 were found to be photochemically inert and show little or no fl uorescence, the excellent properties of poly-1 in regard to electropolymerization, electrochromic response, and fi lm stability prompted us to reexamine its photochemical and photophysical properties.In this contribution, we show that the photochemistry ...

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Section: Methodsmentioning

confidence: 99%

Solvation Dependent Redox‐Gated Fluorescence Emission in a Diarylethene‐Based Sexithiophene Polymer Film

Kortekaas

Browne

2016

Advanced Optical Materials

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“…The electrochemical studies of switchable diarylethene derivatives have been extended to various systems self‐assembled as monolayers on gold electrodes and numerous polymeric films deposited on electrodes and operating as photochemically controlled electroconductive systems .…”

Section: Diarylethene‐based Photoelectrochemical Switchesmentioning

confidence: 99%

Modified Electrodes and Electrochemical Systems Switchable by Light Signals

Katz¹

2018

Electroanalysis

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This article is an overview of extensive research efforts in many laboratories in the last two decades in the area of light‐switchable electrochemical systems and modified electrodes. Electrochemical reactions, including electrocatalytic and bioelectrocatalytic processes, have been reversibly activated and inhibited upon irradiation with light at different wavelengths. In order to realize these light activated or inhibited processes, the electrodes or/and reacting molecules were functionalized with photoisomerizable molecules including various derivatives of diarylethene, phenoxynaphthacenequinone, azobenzene and spiropyran/merocyanine. Photochemical reactions of these species resulted in change of their redox activity, conformation and electrical charge. All these changes affected electrode surfaces or (bio)molecules resulting in switching ON‐OFF corresponding (bio)electrochemical processes. Various systems based on different light‐controlled reactions are reviewed and discussed with specific examples and with many illustrating figures. Possible extensions of the research area and future applications are briefly overviewed in the conclusion section. The present comprehensive review is addressed to a broad scientific community, including newcomers to the area.

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“…In the attempt to bring organic (semi)conducting molecules and photochromic molecules together, several important studies were reported demonstrating that these two varieties of molecules could be mutually advantageous: dyads, multiads, and polymers decorated with photochromic units were synthesized and tested leading to major changes in conductivity and optical properties upon light irradiation [150,157,159,[176][177][178][179][180][181][182].…”

Section: Photochromic Molecules and Organic Semiconductors Incorporatmentioning

confidence: 99%

“…Alongside to the undoubtedly disruptive examples of integration of photochromic molecules into dyads, a remarkable effort has also been devoted to the synthesis of photochromic conjugated conductive polymers as, in principle, any photochromic switching unit conjugated within a π-electron polymer would lead to a modulable conductivity [175,177,178,180,181,184,185]. However, despite the notable advances, these materials suffer from a slow or sometimes even irreversible switching mechanism along with low electrical conductivities.…”

Section: Photochromic Molecules and Organic Semiconductors Incorporatmentioning

confidence: 99%

Hybrid Organic/Photochromic Approaches to Generate Multifunctional Materials, Interfaces, and Devices

Orgiu

Samorı́

2016

Photochromic Materials: Preparation, Properties and Applications

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Silicon industry's greatest strength has always relied on its ability to downscale device dimensions and generate low-cost functions regardless of the relatively high cost per area. Conversely, "van der Waals solids" relying on weak interactions such as organic semiconductors (OSs) have always been thought of complementing this requirement for low-cost production as well as large-area applications by virtue of their characteristic chemical versatility and easy processability. Hence, OSs hold a great potential for the integration in the everyday flexible electronics [1-22] as they feature a number of fundamental properties such as light emission , charge transport , and photovoltaic response .So far, synthetic pathways and processing of organic semiconductors have greatly improved and generated a variety of possible candidate molecules/ processes that are mature enough to meet the initially envisaged applications [97][98][99][100][101][102][103][104][105][106][107][108][109][110][111][112].Nevertheless, the initial desire for reducing the device size is ultimately getting to an end for the Si-based electronics because of the limitations coming from the photolithographic steps involved in the production process of the devices. In this regard, organic and polymer electronics, that is, the electronics based on organic and polymeric semiconductors, cannot complement its inorganic counterpart and the relentless need of miniaturization unless new challenging avenues are pursued.A new strategy can be envisaged in which molecular functions are integrated into organic semiconductors via a controlled combination with an additional molecular component featuring supplementary functions. This is the case of photochromic systems [113][114][115][116][117][118] that are small organic molecules capable of undergoing reversible isomerization upon light irradiation at definite wavelengths between (at least) two (meta)stable states exhibiting markedly different properties at the molecule level. In these molecular switches, the specific isomeric state is selected upon exposure to a light stimulus with a proper wavelength. The most common families of photochromic molecules, depicted in Figure 7.1, Photochromic Materials: Preparation, Properties and Applications, First Edition. Edited by He Tian and Junji Zhang.

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Electrochemical Switching of Conductance with Diarylethene-Based Redox-Active Polymers

Cited by 39 publications

References 57 publications

Solvation Dependent Redox‐Gated Fluorescence Emission in a Diarylethene‐Based Sexithiophene Polymer Film

Solvation Dependent Redox‐Gated Fluorescence Emission in a Diarylethene‐Based Sexithiophene Polymer Film

Modified Electrodes and Electrochemical Systems Switchable by Light Signals

Hybrid Organic/Photochromic Approaches to Generate Multifunctional Materials, Interfaces, and Devices

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