Simple construction of an infrared optically transparent thin-layer electrochemical cell

Krejčík, Michael; Daněk, M.; Hartl, F.

doi:10.1016/0022-0728(91)85012-e

Cited by 957 publications

(769 citation statements)

References 17 publications

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“…This was done in the presence of tetrabutylammonium perchlorate (100 mM) as a supporting electrolyte. The details of the setup were described previously: we used an optically transparent thin-layer electrochemical (OTTLE) cell with 200 mm path length, 28 connected to a potentiostat (Metrohm Autolab PGSTAT 101). 23 The cell consists of a Pt-disk working electrode, a Pt-gauze auxiliary electrode and an Ag-wire as a pseudoreference electrode.…”

Section: Spectroelectrochemistrymentioning

confidence: 99%

Photoinduced ultrafast dynamics of the triphenylamine-based organic sensitizer D35 on TiO2, ZrO2 and in acetonitrile

Oum

Lohse

Klein

et al. 2013

Phys. Chem. Chem. Phys.

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The relaxation dynamics of the dye D35 has been characterized by transient absorption spectroscopy in acetonitrile and on TiO 2 and ZrO 2 thin films. In acetonitrile, upon photoexcitation of the dye via the S 0 -S 1 transition, we observed ultrafast solvation dynamics with subpicosecond time constants.Subsequent decay of the S 1 excited state absorption (ESA) band with a 7.1 ps time constant is tentatively assigned to structural relaxation in the excited state, and a spectral decay with 203 ps time constant results from internal conversion (IC) back to S 0 . On TiO 2 , we observed fast (o90 fs) electron injection from the S 1 state of D35 into the TiO 2 conduction band, followed by a biphasic dynamics arising from changes in a transient Stark field at the interface, with time constants of 0.8 and 12 ps, resulting in a characteristic blue-shift of the S 0 -S 1 absorption band. Several processes can contribute to this spectral shift: (i) photoexcitation induces immediate formation of D35 + radical cations, which initially form electron-cation complexes; (ii) dissociation of these complexes generates mobile electrons, and when they start diffusing in the mesoporous TiO 2 , the local electrostatic field may change; (iii) this may trigger the reorientation of D35 molecules in the changing electric field. A slower spectral decay on a nanosecond timescale is interpreted as a reduction of the local Stark field, as mobile electrons move deeper into TiO 2 and are progressively screened. Multiexponential electron-cation recombination occurs on much longer timescales, with time constants of 30 ms, 170 ms and 1.4 ms. For D35 adsorbed on ZrO 2 , there is no clear evidence for a transient Stark shift, which suggests that initially formed cation-electron (trap state) complexes do not dissociate to form mobile conduction band electrons.Multiexponential decay with time constants of 4, 35, and 550 ps is assigned to recombination between cations and trapped electrons, and also to a fraction of D35 molecules in S 1 which decay by IC to S 0 .Differential steady-state absorption spectra of D35 + in acetonitrile and dichloromethane provide access to the complete D 0 -D 1 band. The absorption spectra of D35 and D35 + are well described by TDDFT calculations employing the MPW1K functional.

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Section: Spectroelectrochemistrymentioning

confidence: 99%

Photoinduced ultrafast dynamics of the triphenylamine-based organic sensitizer D35 on TiO2, ZrO2 and in acetonitrile

Oum

Lohse

Klein

et al. 2013

Phys. Chem. Chem. Phys.

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“…An OTTLE [14] (Optically Transparent Thin Layer Electrochemistry) cell was used during the spectroelectrochemical investigations (Experimental Section).…”

Section: Electrochemistrymentioning

confidence: 99%

(Spectro)electrochemical investigations on (ferrocenyl)thiophenes modified by tungsten Fischer carbenes

Westhuizen¹,

Speck²,

Korb³

et al. 2014

Journal of Organometallic Chemistry

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A series of thiophene tungsten Fischer carbene complexes of type [(CO) 5 W=C(OMe)R] (1, R = 2-Th; 3, R = fcthFc) and [(CO) 5 W=C(OMe)-R'-(OMe)C=W(CO) 5 ] (2, R' = th; 5, R' = fcthfc) was synthesized for investigating low energy charge transfer interactions between the carbene substituents and the transition metal carbonyl fragment incorporating the thiophene heterocyclic system (Th = Thienyl; th = 2,5-thiendiyl; Fc = ferrocenyl; fc = 1,1'-ferrocenediyl).Electrochemical investigations were carried out on these complexes to get a closer insight into the electronic properties of 1, 2, 4 and 5. They reveal reversible one-electron redox events for the 2 ferrocenyl moieties. Moreover, typical electrode reactions could be found for the carbene reductions itself and for the tungsten carbonyl oxidation processes. However, for the thiophene complex 2 two well-separated one-electron reduction events were observed. During the UV-Vis-NIR spectroelectrochemical investigations typical low energy absorptions for the mixed-valent α,α'-diferrocenyl thiophene increment were found, as well as high energy NIR absorptions, which were attributed to metal-metal charge transfer transition between the tungsten carbonyl increment and the ferrocenyl units in the corresponding species. Further infrared spectroelectrochemical studies reveal that the electronic interactions in the corresponding cationic species can be described with weakly coupled class II systems according to Robin and Day.

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“…This band is expected to 10 be highly sensitive to modifications in the ligand donor properties and to changes in the ligand coordination geometry. Spectroelectrochemical measurements using an optically transparent thin layer electrode (OTTLE) cell 21 allowed the electrochemically generated iron(II) complexes to be 15 characterized in situ. For example in complex 7a, a bathochromic shift of the absorption maximum to 536 nm was noted upon reduction.…”

Section: Cobalt(iii) and Iron(iii) Complexesmentioning

confidence: 99%

Organization of spin- and redox-labile metal centers into Langmuir and Langmuir–Blodgett films

et al. 2010

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New sal 2 (trien) ligands that contain alkoxy substituents of various length in meta position of the salicyl entities were coordinated to electronically and magnetically active iron(III) and cobalt(III) centers. The electrochemical and spectroscopic properties of these amphiphilic complexes are 10 virtually unaffected upon alteration of the alkoxy substituents, thus providing a system in which the physical behavior and the metal-centered chemical activity can be tailored independently. The amphiphilic character has been exploited for preparing Langmuir monolayers at the air-water interface and for constructing Langmuir-Blodgett films, hence allowing for hierarchical assembling of electronically and magnetically active systems. While Langmuir films were stable, transfer onto 15 solid supports was limited, which restricted the magnetic analysis of the Langmuir-Blodgett assemblies.

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Simple construction of an infrared optically transparent thin-layer electrochemical cell

Cited by 957 publications

References 17 publications

Photoinduced ultrafast dynamics of the triphenylamine-based organic sensitizer D35 on TiO2, ZrO2 and in acetonitrile

Photoinduced ultrafast dynamics of the triphenylamine-based organic sensitizer D35 on TiO2, ZrO2 and in acetonitrile

(Spectro)electrochemical investigations on (ferrocenyl)thiophenes modified by tungsten Fischer carbenes

Organization of spin- and redox-labile metal centers into Langmuir and Langmuir–Blodgett films

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