UV-Vis-NIR spectroelectrochemistry

Switching of the redox properties of (35-40)a has been examined by means of cyclic voltammetry and UV/Vis/NIR spectroelectrochemistry. For all DHA-VHF couples, we have observed three different I/E (current/potential) responses ... 

Ref [i] Holze R (2008) Surface and interface analysis an electrochemists toolbox. Springer, Berlin [ii] Neudeck A, Marken F, Compton RG (2005) UV/Vis/NIR spectroelectrochemistry. In Electroanalytical Methods. Scholz F (ed), Springer, Berlin, pp 167... 

UV-Vis-NIR spectroelectrochemistry normally allows for a convenient identification of the intervalence charge-transfer band that is crucial for the analysis of electronic interaction, ... 

Mononuclear [W(0)Cl(0Ar)(Tp )] and dinuclear [ W(0)C-(Tp ) 2 (pt-bis(phenolate))] complexes have been synthesized characterized by electrochemistry, EPR, magnetic susceptibility, UV/Vis/NIR spectroelectrochemistry, and X-ray with the aim to evaluate the electronic and magnetic interaction between the redox-active, paramagnetic metal centers.187... 

The simple electronic considerations outlined above show that the bridging ligands play a significant role in the electrochemistry of the dinuelear species described above. This raised the question as to what extent quinonoid forms such as those shown in Figure 6 might be involved in the reduction of the Mo -nitrosyl and the oxidation of the Mo xo eomplexes, respectively. UV/Vis/NIR spectroelectrochemistry provided useful insights into this beeause the electronic transitions in the two extreme canonical forms are expected to be quite different. 

Figure 14.3 UV-vis-NIR spectroelectrochemistry of a mixed valence metal complex, reproduced from reference (20) with permission from The Royal Society of Chemistry.

Using a series of new coordination compounds of some platinum group metals with potentially hemilabile redox-active chelate ligands based on the o-benzosemiquinoneimine intermediate, the extent of noninnocent behavior has been established experimentally, via structure determination and EPR, UV-vis-NIR spectroelectrochemistry [35, 36], and computationally... 

Refs. [i] Eigen M (1954) Discuss Faraday Soc 17 194 [ii] Norrish RGW, Porter G (1949) Nature 164 658 (1952) Proc RSocA 210 439 [Hi] Dian EW-G, Herek JL, Kim ZH, Zewail AH (1999) Science 279 847 [iv] Bard A] (1992) Pure Appl Chem 64 185 [v] Bard A], Fan F-R, Mirkin MV (1994) Scanning electrochemical microscopy. In Bard A] (ed) Electroanalytical chemistry, vol. 18. Marcel Dekker, New York [vi] Neudeck A, Marken F, Compton RG (2002) UV/Vis/NIR spectroelectrochemistry. In Scholz F (ed) Electroanalytical methods. Springer, Berlin, pp 167-189 [vii] FeldbergSW, Newton MD, Smalley JF (2004) The indirect laser-induced temperature jump methodefor characterizing fast interfacial electron tranter concept, application, and results. In Bard A], Rubinstein I (eds) Electroanalytical chemistry, vol. 22. Marcel Dekker, New York, pp 101-180... 

In conclusion, UV/Vis/NIR spectroelectrochemistry in both transmission and reflection mode are extremely useful techniques that yield a wealth of complementary data additional to those obtained in pure electrochemical voltam-metric experiments. Especially when based on computer simulation models, this data may be used to unravel the kinetics and thermodynamics of complex electrode processes. 

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