Synthesis and Properties of Dinuclear Complexes with a Photochromic Bridge: An Intervalence Electron Transfer Switching “On” and “Off”

Fraysse, Sandrine; Coudret, Christophe; Launay, Jean‐Pierre

doi:10.1002/1099-0682(200007)2000:7<1581::aid-ejic1581>3.0.co;2-2

Cited by 223 publications

(136 citation statements)

References 33 publications

Supporting

Mentioning

131

Contrasting

Order By: Relevance

“…The diarylethene class of photochromic switches, in contrast to spiropyrans, exists in two thermally stable forms: the so-called open, colorless form and the closed, colored form ( Figure 5). Despite extensive studies on the photochemistry of the dithienylcyclopentene class of photoswitchable compounds (21), only relatively recently has the electrochromic and general electrochemical behavior of this important class of molecular switches received a similar level of attention (22)(23)(24)(25)(26)(27).…”

Section: Figurementioning

confidence: 99%

Light Switching of Molecules on Surfaces

Browne

Feringa

2009

Annu. Rev. Phys. Chem.

274

254

View full text Add to dashboard Cite

Smart surfaces, surfaces that respond to an external stimulus in a defined manner, hold considerable potential as components in molecular-based devices, not least as discrete switching elements. Many stimuli can be used to switch surfaces between different states, including redox, light, pH, and ion triggers. The present review focuses on molecular switching through the electronic excitation of molecules on surfaces with light. In developing light-responsive surfaces, investigators face several challenges, not only in achieving high photostationary states and fully reversible switching, but also in dealing with fatigue resistance and the effect of immobilization itself on molecular properties. The immobilization of light-responsive molecules requires the design and synthesis of functional molecular components both to achieve light switching and to anchor the molecular entity onto a surface. This review discusses several demonstrative examples of photoswitchable molecular systems in which the photochemistry has been explored in the immobilized state under ambient conditions and especially on electroactive surfaces, including self-assembled monolayers, bilayers, and polymer films.

show abstract

Section: Figurementioning

confidence: 99%

Light Switching of Molecules on Surfaces

Browne

Feringa

2009

Annu. Rev. Phys. Chem.

274

254

View full text Add to dashboard Cite

show abstract

“…11 As long as the 70 dithienylethene (DTE) bridge is in its open form (2o), there is no evidence for any interaction between the two ruthenium units, but upon photoisomerization to the closed DTE form (2c), an intervalence absorption band becomes detectable. 75 Analysis of the IVCT band with Hush theory yields HAB = 200 cm -1 , which is a relatively high value given the large spatial separation (> 23 Å) between the two redox-active metal centers.…”

Section: Dithienylethenes As Photoswitchable Unitsmentioning

confidence: 99%

“…9 Mixed valence compounds with molecular bridges comprised of units that can undergo reversible 45 photoisomerization reactions are well suited, simple model systems for investigating how charge delocalization can be affected with light. The first three reports on photoswitchable mixed valence appeared in 1996 and 2000, [10][11][12] but then this field of research has been dormant until 2006, when it finally 50 experienced a revival. 13 This tutorial review reports on the most significant findings from this emerging field, with particular focus on the contributions made by the groups of Launay, Akita, Nishihara, and the author's own research team.…”

mentioning

confidence: 99%

Photoswitchable mixed valence

Wenger

2012

Chem. Soc. Rev.

View full text Add to dashboard Cite

For a molecular electronics technology to be fully serviceable, switching functions will be indispensable. 5 Specifically, it will be desirable to control the conductivity of a given molecule using an external stimulus. Photoswitchable mixed valence systems are comprised of a reversibly photoisomerizable bridging unit connecting two redox-active moieties, and as such represent some of the most simple chemical systems in which switching of charge delocalization can be explored. As photoisomerizable units, dithienylethenes have received much attention in the context of photoswitchable mixed valence, but 10 there are also more exotic examples such as norbornadiene-and dimethyldihydropyrene-based switchable systems. As redox-active units responsible for the mixed valence phenomenon, both metal-containing as well as purely organic moieties have been employed. Typical investigations in this area involve the comparison of cyclic voltammograms and (near-infrared) optical absorption spectra of the two isomeric forms of a given system. The magnitude of the comproportionation constant and evaluation of 15 intervalence absorption bands using appropriate theoretical models yield information regarding the extent of charge delocalization in the two isomeric forms. In several of the compounds investigated so far, the light stimulus induces a substantial increase of charge delocalization, or in the terminology commonly used in mixed valence chemistry, a changeover from class I to class II or even class III behavior.

show abstract

“…In this way, switches can be made by chemically or physically changing the molecular conformation or the metal-metal separation, as well as, by tuning the degree of the electronic coupling through the redox and/or acid-base properties of spacer. [27][28][29][30][31][32][33] Another way of controlling metal-metal interactions is based on the differential solvent effects on the metal complexes. 34,35 A simple and efficient pH-induced molecular "on/off" switching has been recently devised based on a symmetric bridged ruthenium dimer, [(edta)Ru(µ-L)Ru(edta)] n-, where n = 3, or 4, and L = benzotriazolate ligand, by exploiting its unusual mixed-valence state behavior as a function of the pH.…”

Section: Proton-induced Molecular Switchingmentioning

confidence: 99%

Molecular Materials and Devices: Developing New Functional Systems Based on the Coordination Chemistry Approach

Toma

2004

ChemInform

View full text Add to dashboard Cite

Neste limiar da era nanotecnológica, o planejamento molecular dos materiais e os estudos de moléculas isoladas estão abrindo imensas possibilidades no emprego de sistemas moleculares em dispositivos eletrônicos e fotônicos, bem como em aplicações tecnológicas baseadas em propriedades de chaveamento ou reconhecimento molecular. Com esse escopo, os químicos inorgânicos em particular, podem aplicar com vantagens as estratégias proporcionadas pela química de coordenação, para construir nanomateriais funcionais que permitam a exploração das propriedades dos centros metálicos e das características dos ligantes presentes. A química de coordenação também oferece recursos eficientes na auto-montagem de nanoestruturas, baseadas na especificidade da interação metal-ligante e nas características estereoquímicas dos complexos. Diversos materiais moleculares gerados a partir de compostos inorgânicos e metal-orgânicos são focalizados neste artigo, com ênfase em novas porfirinas e porfirazinas supramoleculares, clusters e complexos metálicos. Tais sistemas também são enfocados sob o ponto de vista de suas aplicações em catálise, sensores e dispositivos moleculares.At the onset of the nanotechnology age, molecular designing of materials and single molecule studies are opening wide possibilities of using molecular systems in electronic and photonic devices, as well as in technological applications based on molecular switching or molecular recognition. In this sense, inorganic chemists are privileged by the possibility of using the basic strategies of coordination chemistry to build up functional supramolecular materials, conveying the remarkable chemical properties of the metal centers and the characteristics of the ancillary ligands. Coordination chemistry also provides effective self-assembly strategies based on specific metal-ligand affinity and stereochemistry. Several molecular based materials, derived from inorganic and metal-organic compounds are focused on this article, with emphasis on new supramolecular porphyrins and porphyrazines, metal-clusters and metal-polyimine complexes. Such systems are also discussed in terms of their applications in catalysis, sensors and molecular devices.

show abstract

Synthesis and Properties of Dinuclear Complexes with a Photochromic Bridge: An Intervalence Electron Transfer Switching “On” and “Off”

Cited by 223 publications

References 33 publications

Light Switching of Molecules on Surfaces

Light Switching of Molecules on Surfaces

Photoswitchable mixed valence

Molecular Materials and Devices: Developing New Functional Systems Based on the Coordination Chemistry Approach

Contact Info

Product

Resources

About