Noncovalent Dualism in Perylene-Diimide-Based Keggin Anion Complexes: Theoretical and Experimental studies.

We report the synthesis and comprehensive characterization of organic-inorganic hybrid salts formed by bis-cationic N,N'-bis(2-(trimethylammonium)ethylene)perylene-3,4,9,10-tetracarboxylic acid bisimide (PTCD2+) and Keggin-type [XW12O40]n- (X = Si, n = 4; X = P, n = 3) polyoxometalates. (PTCD)3[PW12O40]2·3DMSO·2H2O (2) and (PTCD)2[SiW12O40]·DMSO·2H2O (3) were structurally characterized by single crystal X-ray diffraction. The cations in both structures exhibited infinite chainlike arrangements through π-π interactions, contrasting with the previously reported cation-anion stacking observed in naphthalene diimide derivatives. A detailed theoretical study employing topological analysis of the electron density distribution within the quantum theory of atoms in molecules approach provided further insights into this structural dualism. Atomic force microscopy analyses revealed the formation of self-assembled supramolecular structures on graphite from molecular monolayers (3 nm of thick) to submicrometer aggregates for 2. Hyperspectral Raman spectroscopy imaging revealed that such heterostructures are likely formed by an enhanced π-π interactions. Both complexes demonstrated interesting electrochemical behavior, photoluminescence and X-ray-induced luminescence. Electron spin resonance analysis confirmed charge separation in both compounds, with enhanced efficiency observed in compound 2. Our findings of these perylene-based organic-inorganic hybrid salts offer the potential for their application in optoelectronic devices and functional materials.

Trapping of Ag+ into a Perfect Six-Coordinated Environment: Structural Analysis, Quantum Chemical Calculations and Electrochemistry.

Self-assembly of (Bu4N)4[ß-Mo8O26], AgNO3, and 2-bis[(2,6-diisopropylphenyl)-imino]acenaphthene (dpp-bian) in DMF solution resulted in the (Bu4N)2[ß-{Ag(dpp-bian)}2Mo8O26] (1) complex. The complex was characterized by single crystal X-ray diffraction (SCXRD), X-ray powder diffraction (XRPD), diffuse reflectance (DR), infrared spectroscopy (IR), and elemental analysis. Comprehensive SCXRD studies of the crystal structure show the presence of Ag+ in an uncommon coordination environment without a clear preference for Ag-N over Ag-O bonding. Quantum chemical calculations were performed to qualify the nature of the Ag-N/Ag-O interactions and to assign the electronic transitions observed in the UV-Vis absorption spectra. The electrochemical behavior of the complex combines POM and redox ligand signatures. Complex 1 demonstrates catalytic activity in the electrochemical reduction of CO2.

Coordination of Pt(IV) by {P8W48} Macrocyclic Inorganic Cavitand: Structural, Solution, and Electrochemical Studies.

Hydrothermal reaction of a macrocyclic inorganic POM cavitand Li17(NH4)21H2[P8W48O184] with [Pt(H2O)2(OH)4] results in coordination of up to six {Pt(H2O)x(OH)4-x} fragments to the internal surface of the polyoxoanion. The product was isolated as K22(NH4)9H3[{Pt(OH)3(H2O)}6P8W48O184]·79H2O (1) and characterized by multiple techniques in the solid state (SCXRD, XRPD, XPS, FTIR, and TGA) and in solution (NMR, ESI-MS, and HPLC-ICP-AES). Electrochemical properties were studied both in solution and as components of the paste electrode. The complex shows electrocatalytic activity in water oxidation.

Self-assembly patterns of non-metalloid silver thiolates: structural, HR-ESI-MS and stability studies.

Screening of AgNO3/AgStBu solutions in DMF, DMSO and NMP resulted in the isolation of three novel nanosized silver/thiolate complexes with a torus-like {Ag20(StBu)10} core. The structures of [NO3@Ag20(StBu)10(NO3)9(DMF)6] (1) and [NO3@Ag20(tBuS)10(NO3)8(NMP)8][NO3@Ag19(tBuS)10(NO3)8(NMP)6]2(NO3) (2) were studied by single crystal X-ray diffraction (SCXRD). The self-assembly process leading to 1 can be switched to a different outcome using Br-, resulting in [Br@Ag16(StBu)8(NO3)5(DMF)3](NO3)2 (3), which is the one of the few genuine host-guest complexes in the silver/thiolate systems. Solutions of the individual complexes in CH3CN were studied by HR-ESI-MS techniques, which revealed a dynamic behavior for each complex, driven by a redistribution of the {AgNO3} units. This dynamics results in the appearance of both cationic and anionic species, based on unchanged silver-thiolate cores. Daylight causes degradation of 3 with the formation of a composite material based on defective orthorhombic Ag2S with a porous morphology, as observed using the SEM technique. The electrocatalytic HER activity of such a material was studied.

Lanthanides as NMR probes of fast molecular dynamics at high magnetic fields and temperature sensors: conformational interconversion of erbium ethylenediaminetetraacetate complexes.

(1)H NMR measurements are reported for D2O solutions of paramagnetic complex [Er(H2O)(EDTA(4-))](-) (I) for temperature interval 273-319 K. Diamagnetic complex [Lu(H2O)(EDTA(4-))](-) (II) was used as an NMR reference compound. The spectra obtained have been analyzed using a band-shape analysis technique in the framework of dynamic NMR (DNMR) taking into account the temperature dependence of lanthanide-induced shifts. Intramolecular dynamics in I was assigned to the interconversion of Δ-λE-δδδδ and Δ-δE-δδδδ conformers with estimated activation free energy ΔG(‡)(298 K) = 50 ± 4 kJ/mol. The methodology of paramagnetic 4f-element probe applications on the example of Er(3+) for the study of free-energy changes in chemical exchange processes, as well as the advantages of this method in comparison with DNMR studies of diamagnetic substances, is discussed. In accordance with the literature reviewed, the fulfilled experimental study is the first example of intramolecular dynamics determination for erbium complexes. An additional advantage of the investigation is in the approach proposed which extends the range of measurement of the NMR rate constants for paramagnetic 4f-element complexes compared to diamagnetic ones. Coordination compounds investigated represent a new type of thermometric NMR sensors and lanthanide paramagnetic probes for in situ temperature control in solutions.

Destruction of EDTA using Ce(IV) mediated electrochemical oxidation: a simple modeling study and experimental verification.

Mediated electrochemical oxidation (MEO) is a recent development in the environmental research field for the complete destruction of organic pollutants. This study presents the destruction of EDTA by cerium(IV) MEO process in nitric acid medium. The destruction reaction was carried out in a continuous stirred tank reactor under various conditions. A simple kinetic model was developed to analyze and simulate the organic destruction in the MEO process. The model was based on the calculation of the total mass balance, the component mass balance, and the energy balance in the reactor and also in the heating jacket. The sensitivity to key operating conditions such as the initial EDTA concentration (50-200 mM), EDTA feeding time (30-180 min), reaction temperature (323-363 K), and the rate laws corresponding to zero-, first-, second-, and third-order reaction were analyzed. It was found that the model simulated agreed well with the experimental data for EDTA oxidation. The results obtained showed the suitability of the MEO process for the effective mineralization of high concentrations of EDTA.