Hydroquinone-Quinone Redox Switch

The hydroquinone-quinone redox couple was used in a device to electro-chemically switch between linear conjugation and cross-conjugation in the oligo(phenylenevinylene) (OPV) molecular wires 68 and 69, respectively (Scheme 9.11) [47]. After inserting the molecule in an octanethiolate self-assembled monolayer (SAM) on gold, an electrochemical potential was employed to switch between the quinone and hydroquinone. Electrochemical STM was used to control the oxidation state and to measure the electrical conductivity... 

Fluorescent redox switches based on compounds with electron acceptors and fluorophores have been also reported. For instance, by making use of the quinone/ hydroquinone redox couple a redox-responsive fluorescence switch can be established with molecule 19 containing a ruthenium tris(bpy) (bpy = 2,2 -bipyridine) complex.29 Within molecule 19, the excited state of the ruthenium center, that is, the triplet metal-to-ligand charge transfer (MLCT) state, is effectively quenched by electron transfer to the quinone group. When the quinone is reduced to the hydroquinone either chemically or electrochemically, luminescence is emitted from the ruthenium center in molecule 19. Similarly, molecule 20, a ruthenium (II) complex withhydroquinone-functionalized 2,2 6, 2"-terpyridine (tpy) and (4 -phenylethynyl-2,2 6, 2"- terpyridine) as ligands, also works as a redox fluorescence switch.30... 

Quinones represent an important class of compound that undergo proton-coupled electron transfer reactions [35]. The order and kinetics of the two-electron/two-proton redox reactions of the quinone (Q)/hydroquinone (H2Q) couple continue to be active subjects of investigation. The interconversion of Q to H2Q can involve up to seven different intermediates depending on the pH of the solution and the solvent. However, in low-pH electrolytes electrochemically reversible behavior can be observed despite the significant changes that accompany redox switching. Beyond... 

Transfer of calcium cations (Ca2 + ) across membranes and against a thermodynamic gradient is important to biological processes, such as muscle contraction, release of neurotransmitters or biological signal transduction and immune response. The active transport can be artificially driven (switched) by photoinduced electron transfer processes (Section 6.4.4) between a photoactivatable molecule and a hydroquinone Ca2 + chelator (405) (Scheme 6.194).1210 In this example, oxidation of hydroquinone generates a quinone to release Ca2+ to the aqueous phase inside the bilayer of a liposome, followed by reduction of the quinone back to hydroquinone to complete the redox loop, which results in cyclic transport of Ca2 +. The electron donor/acceptor moiety is a carotenoid porphyrin naphthoquinone molecular triad (see Special Topic 6.26). 

To explain the observations, the reader s attention is to be switched to the reversible redox processes known for the pair of hydroquinone and quinone (denoted hereafter shortly QH and Q), which can be described as follows [18] ... 

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