NIR spectroelectrochemistry has scarcely been used for deconvolving aqueous mixtures due to the water restriction in this spectral range. However, this work offers an interesting approach for the study of mixtures of molecules with similar electrochemical and spectroscopic behaviour by overcoming the limitations of this hybrid technique. As a proof of concept, the resolution of mixtures of two dyes with similar chemical structures demonstrates the usefulness of NIR spectroelectrochemistry.
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http://dx.doi.org/10.1039/c9cp00484j | DOI Listing |
J Am Chem Soc
January 2025
Chemistry Research Laboratory, Department of Chemistry, University of Oxford, Oxford OX1 3TA, U.K.
The delocalization length of charge carriers in organic semiconductors influences their mobility and is an important factor in the design of functional materials. Here, we have studied the radical anions of a series of linear and cyclic butadiyne-linked porphyrin oligomers using CW-EPR, H Mims ENDOR and NIR/MIR spectroelectrochemistry together with DFT calculations and multiscale molecular modeling. Low-temperature hyperfine EPR spectroscopy and optical data show that polarons are delocalized nonuniformly over about four porphyrins with most of the spin density on just two units even in the cyclic structures, in which all porphyrin sites are identical.
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December 2024
Univ Rennes, CNRS, ISCR (Institut des Sciences Chimiques de Rennes) - UMR 6226, F-35000 Rennes, France.
Bi- and trimetallic platinum(bipyridine)(dithiolene) complexes involving different organic linkers between the redox active platinum(dithiolene) moieties have been synthesized and studied by electrochemistry and spectroelectrochemistry. Cyclic voltammetry experiments carried out on these multinuclear complexes in dichloromethane using [NBu][PF] as the supporting salt show only one oxidation process involving the metallacycles. Nevertheless, spectro-electrochemical studies, carried out under the same conditions, show a different evolution of the spectra during oxidation depending on the position of the metallacycles on the phenyl ring.
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October 2024
Radioisotope Science and Technology Division, Oak Ridge National Laboratory, 1 Bethel Valley Rd., Oak Ridge, Tennessee 37831, United States.
In situ optical spectroscopy, spectropotentiometry, and multivariate analysis were applied to the Np(IV) nitrate system to better understand speciation and quantify HNO concentration. Thin-layer spectropotentiometry, or spectroelectrochemistry, was leveraged to isolate and stabilize Np(IV) without compromising the solution conditions and generate representative Vis-NIR absorption spectra from 0.5 to 10 M HNO and benchmark the corresponding Np(IV) molar absorptivity coefficients.
View Article and Find Full Text PDFMolecules
September 2024
Faculty of Chemistry, Adam Mickiewicz University in Poznań, Uniwersytetu Poznańskiego 8, 61-614 Poznań, Poland.
The azomethine with a donor-acceptor-acceptor-acceptor-donor structure has been synthesized and characterized. Azomethine exhibited luminescence properties and a positive solvatochromic effect. Electropolymerization on terminated triphenylamine groups was used to obtain a thin layer of the polyazomethine .
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October 2024
Laboratory for Zero-Carbon Energy, Institute of Innovative Research, Tokyo Institute of Technology, 2-12-1 N1-32, O-okayama, Meguro-ku, 152-8550 Tokyo, Japan.
Combination of a uranyl(VI) ion (UO) with a redox-active ligand results in characteristic electronic structures that cannot be achieved by either component alone. In this study, three UO complexes that bear symmetric or asymmetric 2,6-diiminopyridine-based ligands were synthesized and found to exhibit a first redox couple between -1.17 V and -1.
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