Molecular charge-transfer complexes of three N-aryl-N'-isopropyloxycarbonylsulfamides derivatives with π-acceptors tetracyanoethylene (TCNE), and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), were studied by using zero and second order derivative UV spectrophotometry in different solvents at four different temperatures within the range of 20-35 °C. The stoichiometries of the complexes were found to be 1:1 ratio between donors and acceptors using Job's method. The data were analyzed in terms of their stability constant (K), molar extinction coefficient (εCT), thermodynamic standard reaction quantities (ΔG°, ΔH°, ΔS°), oscillator strength (f), transition dipole moment (μEN) and ionization potential (ID). The results show that the stability constant (K) for the complexes was found to be dependant upon the nature of electron acceptor, electron donor, and polarity of used solvents.
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http://dx.doi.org/10.1016/j.saa.2013.01.083 | DOI Listing |
Dalton Trans
January 2025
College of Chemical Engineering, State Key Laboratory Breeding Base of Green-Chemical Synthesis Technology, Zhejiang University of Technology, Hangzhou, Zhejiang 310014, P. R. China.
A series of carbazolylpyridine ()-based 6/5/6 Pt(II) complexes featuring tetradentate ligands with nitrogen or oxygen atoms as bridging groups was designed and synthesized, and the bridging nitrogen atoms were derived from acridinyl (Ac), azaaceridine (AAc) and carbazole (Cz). Systematic experimental and theoretical studies reveal that the ligand structures have a significant effect on the electrochemical, photophysical and excited state properties of these complexes. Their oxidation processes mainly occur on the carbazole-Pt moieties, whereas the reduction processes typically occur on the electron-deficient pyridine (Py) moieties.
View Article and Find Full Text PDFAnal Chem
January 2025
Departamento de Química Física, Facultad de Química, Regional Campus of International Excellence "Campus Mare Nostrum", Universidad de Murcia, Murcia 30100, Spain.
Electrochemistry in confined environments, that is, involving experimental configurations with spatial restrictions that affect the overall mass transport, is becoming a very attractive way of carrying out electroanalytical measurements for sensing, especially for the so-called thin-layer (TL) configuration, which ideally allows the complete conversion of the analytes under study in small volumes and short times. To improve the understanding of this kind of situation, general expressions for the current-potential-time and charge-potential-time responses of charge transfer processes taking place under finite diffusion conditions with two different configurations (no mass renovation, bounded diffusion; and effective mass renovation, unbounded diffusion) are discussed in this work. By using these expressions, it is possible to establish accurate limits for the attainment of TL conditions and to conclude that for bounded conditions, the charge is a more adequate quantity for electroanalytical purposes.
View Article and Find Full Text PDFSmall
January 2025
School of Chemical and Biological Engineering, Institute of Chemical Process (ICP), Institute of Engineering Research, Seoul National University, 1 Gwanak-ro, Gwanak-gu, Seoul, 08826, Republic of Korea.
As an oxidant, the ferryl-oxo complex (Fe═O) offers excellent reactivity and selectivity for degrading recalcitrant organic contaminants. However, enhancing Fe═O generation on heterogeneous surfaces remains challenging because the underlying formation mechanism is poorly understood. This study introduces edge defects onto a single-atom Fe catalyst (FeNC-edge) to promote Fe═O generation via peroxymonosulfate (PMS) activation.
View Article and Find Full Text PDFSmall
January 2025
Beijing Key Laboratory for Green Catalysis and Separation and Department of Chemical Engineering, College of Materials Science and Engineering, Beijing University of Technology, Beijing, 100124, P. R. China.
Metal-organic frameworks (MOFs) are rigorously investigated as promising candidates for CO capture and conversion. MOF-on-MOF heterostructures integrate bolstered charger carrier separation with the intrinsic advantages of MOF components, exhibiting immense potential to substantially escalate the efficiency of photocatalytic CO reduction (CORR). However, the structural and compositional complexity poses significant challenges to the controllable development of these heterostructures.
View Article and Find Full Text PDFChem Commun (Camb)
January 2025
Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA.
An isostructural series of four annulated actinocene complexes, M(hdcCOT) (M = Th, U, Np, Pu), is reported. The syntheses proceed through a trivalent starting material when M = U, Np, Pu with subsequent oxidation or, in the case of M = Th, directly from ThCl(DME). X-ray crystallography shows that each actinocene has molecular point symmetry in the solid state, with the metal atoms symmetrically bonded to two 10π-aromatic [8]annulene dianion rings.
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