Deciphering Electronic and Structural Effects in Copper Corrole/Graphene Hybrids.

Non-covalent hybrid materials based on graphene and A3 -type copper corrole complexes were computationally investigated. The corroles complexes contain strong electron-withdrawing fluorinated substituents at the meso positions. Our results show that the non-innocent character of corrole moiety modulates the structural, electronic, and magnetic properties once the hybrid systems are held. The graphene-corrole hybrids displayed outstanding stability via the interplay of dispersion and electrostatic driving forces, while graphene act as an electron reservoir. The hybrid structures exposed an intriguing magneto-chemical performance, compared to the isolated counterparts, that evidenced how structural and electronic effects contributed to the magnetic response for both ferromagnetic and antiferromagnetic cases. Directional spin polarization and spin transfer from the corrole to the graphene surface participate in the amplification. Finally, there are relations between the spin transfer, the magnetic response, and the copper distorted ligand field, offering exciting hints about modulating the magnetic response. Therefore, this work shows that copper corroles emerged as versatile building blocks for graphene hybrid materials, especially in applications requiring a magnetic response.

Alkylated Benzodithienoquinolizinium Salts as Possible Non-Fullerene Organic N-Type Semiconductors: An Experimental and Theoretical Study.

Three photobicyclized benzodithienoquinolizinium tetrafluoroborates (BPDTQBF4) were prepared and evaluated by UV-Vis and fluorescence spectral, electrochemical analysis, and by theoretical calculations as possible organic n-type semiconductors. Evaluation and comparison of their LUMO levels, HOMO-LUMO energy gaps as monomeric and π-stacked dimers with those of other materials, suggest their potential as organic n-type semiconductors. Calculations of their relative charge carrier mobilities confirmed this potential for one derivative with a long (C-14) alkyl chain appended to the polycyclic planar π-system.

Data of interaction of supported ionic liquids phases onto copper nanoparticles: A density functional theory study.

This work contains data on the computational, structural, and electronic characterization of supported ionic liquids phases anchored to copper nanoparticles using Density Functional theory calculations. The data supplement the paper "Interaction of supported ionic liquids phases onto copper nanoparticles: A Density Functional Theory study" [1], based on the adsorption of ionic liquid onto a Cu nanoparticle is analyzed from a chemical and physical point of view. The chemical analysis is based on Atoms in Molecule theory (AIM) and allows us to differentiate the chemical binding nature between ionic liquid and copper nanoparticle. On the other hand, the energy decomposition analysis based on absolutely localized molecular orbital (ALMO-EDA) describes the physical contributions that govern the interaction between ionic liquid and the copper nanoparticles. Herein, detailed and extended information in the synthesis and computational characterization are presented.

Correction: Highly modulated supported triazolium-based ionic liquids: direct control of the electronic environment on Cu nanoparticles.

[This corrects the article DOI: 10.1039/D0NA00055H.].

Highly modulated supported triazolium-based ionic liquids: direct control of the electronic environment on Cu nanoparticles.

A series of new triazolium-based supported ionic liquids (SILPs), decorated with Cu NPs, were successfully prepared and applied to the N-arylation of aryl halides with anilines. The triazoles moieties were functionalised using copper-catalysed azide-alkyne cycloaddition. SILP surface characterisation showed a strong correlation between the triazolium cation volume and textural properties. STEM images showed well-dispersed Cu NPs on SILPs with a mean diameter varying from 3.6 to 4.6 nm depending on the triazolium cation used. Besides, XPS results suggest that the Cu(0)/Cu(i) ratio can be modulated by the electronic density of triazolium substituents. XPS and computational analysis gave mechanistic insights into the Cu NP stabilisation pathways, where the presence of electron-rich groups attached to a triazolium ring plays a critical role in leading to a cation adsorption pathway (E ads = 72 kcal mol-1). In contrast, less electron-rich groups favour the anion adsorption pathway (E ads = 63 kcal mol-1). The Cu@SILP composite with electron-rich groups showed the highest activity for the C-N Ullmann coupling reaction, which suggests that electron-rich groups might act as an electron-like reservoir to facilitate oxidative addition for N-arylation. This strategy firmly suggests the strong dependence of the nature of triazolium-based SILPs on the Cu NP surface active sites, which may provide a new environment to confine and stabilise MNPs for catalytic applications.

Interaction of H2O with (CuS)n, (Cu2S)n, and (ZnS)n small clusters (n = 1-4, 6): relation to the aggregation characteristics of metal sulfides at aqueous solutions.

The interaction of H2O onto small CuS, Cu2S, and ZnS clusters was theoretically studied by Density Functional Theory computations to get insights into the aggregation characteristics of metal sulfides at aqueous solutions. The results show the charge-controlled interactions with polarized solvent molecules are favored on the ZnS clusters compared with CuS and Cu2S clusters. Moreover, the chemical adsorption of H2O molecules is energetically favored onto ZnS clusters with higher interaction energies of up to 35.4 kcal/mol compared with CuS and Cu2S clusters (up to 31.3 kcal/mol), where the stability of H2O adsorption decreases as the size of the clusters increases. However, thermochemical analysis shows that the adsorption of H2O on copper sulfides is not a spontaneous process at room temperature. Additionally, the electrostatic energy of H2O onto the Cu2S and CuS clusters is lower than that associated with the H2O-H2O interactions, suggesting that copper precipitates prefer to bind between them at early stages of the precipitation process due to an unfavorable solvent-solute interaction. Dispersion forces play a relative key role in the interaction of water on copper sulfides, while for zinc sulfide clusters, the adsorption energy is slightly influenced by dispersion contributions. Accordingly, the aggregation of zinc sulfides in a water environment is expected to be lower compared with copper sulfides, and where the aggregation characteristics are not determined by the binding energy of the sulfides, but of the ability to interact with the solvent molecules. These statements were confirmed by experimental optical microscopy analysis and settling tests during precipitation processes in water. Therefore, this work allows proposing a simple strategy to study the aggregation characteristics of metal sulfides, which turns useful for use in hydrometallurgical applications.

Substitution Effect on the Charge Transfer Processes in Organo-Imido Lindqvist-Polyoxomolybdate.

Two new aromatic organo-imido polyoxometalates with an electron donor triazole group ([n-Bu4N]2[Mo6O18NC6H4N3C2H2]) (1) and a highly conjugated fluorene ([n-Bu4N]2[Mo6O18NC13H9]) (2) have been obtained. The electrochemical and spectroscopic properties of several organo-imido systems were studied. These properties were analysed by the theoretical study of the redox potentials and by means of the excitation analysis, in order to understand the effect on the substitution of the organo-imido fragment and the effect of the interaction to a metal centre. Our results show a bathochromic shift related to the charge transfer processes induced by the increase of the conjugated character of the organic fragment. The cathodic shift obtained from the electrochemical studies reflects that the electronic communication and conjugation between the organic and inorganic fragments is the main reason of this phenomenon.

pH-Controlled Assembly of 3D and 2D Zinc-Based Metal-Organic Frameworks with Tetrazole Ligands.

We report the synthesis and structural diversity of Zn(II) metal-organic framework (MOF) with in situ formation of tetrazole ligand 3-ptz [3-ptz = 5-(3-pyridyl)tetrazolate] as a function pH. By varying the initial reaction pH, we obtain high-quality crystals of the noncentrosymmetric three-dimensional MOF Zn(3-ptz)2 , mixed phases involving the zinc-aqua complex [Zn(H2O)4(3-ptz)2]·4H2O, and two-dimensional MOF crystals Zn(OH)(3-ptz) with a tunable microrod morphology, keeping reaction time, temperature, and metal-ligand molar ratio constant. Structures are characterized by X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, and UV-vis spectroscopy. We discuss the observed structural diversity in terms of the relative abundance of hydroxo-zinc species in solution for different values of pH.

The first ReI organometallic complex with an organoimido-polyoxometalate ligand.

The spectroscopic, electrochemical and photophysical properties of the first ReI organometallic organoimido-polyoxometalate complex [n-Bu4N][Mo6O18NC6H4-CH2-N3C2H2-Re-phen(CO)3] compared with all fragments are reported. The UV-Vis spectra are analysed using experimental and theoretical tools. In contrast to the reported studies in the literature, our results show that a new more intense band is present in the spectra of the hybrid ligand obscuring the intra-polyanion charge transfer. The electrochemical results show that the strong acceptor character of the polyoxometalate fragment is quenched by the condensation of the phenyl-triazole molecule.