Unconventional C-Hlg···H-C (Hlg = Cl, Br, and I) Interactions Involving Organic Halides: A Theoretical Study.

In this study, unconventional C-Hlg···H-C (Hlg = Cl, Br, and I) interactions involving sp, sp, and sp organic halides were investigated at the RI-MP2/aug-cc-pVQZ level of theory. Energy Decomposition Analyses (EDA) and Natural Bonding Orbital (NBO) studies showed that these intermolecular contacts are mainly supported by orbital and dispersion contributions, which counteracted the unfavorable/slightly favorable electrostatics due to the halogen-hydrogen σ-hole facing. In addition, the Bader's Quantum Theory of Atoms in Molecules (QTAIM) and the Noncovalent Interaction plot (NCIplot) visual index methodologies were used to further characterize the interactions discussed herein.

Aluminum Fluorides as Noncovalent Lewis Acids in Proteins: The Case of Phosphoryl Transfer Enzymes.

The Protein Data Bank (PDB) was scrutinized for the presence of noncovalent O ⋅ ⋅ ⋅ Al Triel Bonding (TrB) interactions, involving protein residues (e. g. GLU and GLN), adenosine/guanine diphosphate moieties (ADP and GDP), water molecules and two aluminum fluorides (AlF and AlF ).

On the influence of metal nanoparticle and π-system sizes in the stability of noncovalent adducts: a theoretical study.

Herein we have computationally evaluated the relationship between Ag and Au nanoparticle (Ag/AuNP) size and π-surface extension in the formation of noncovalent complexes at the PBE0-D3/def2-TZVP level of theory. The NP-π interaction is known in supramolecular chemistry as a Regium-π bond (Rg-π), and differentiates from classical coordination bonds in strength and type of metal orbitals involved. In this study, the Rg-π complexes involved small Ag/AuNPs composed by 1 to 5 atoms and benzene, naphthalene and anthracene as π-systems, being characterized using several molecular modeling tools, including molecular electrostatic potential (MEP) calculations, energy decomposition analysis (EDA), quantum theory of atoms in molecules (QTAIM), non covalent interaction plot (NCIplot) and natural bonding orbital (NBO) methodologies.

From Coordination to π-Hole Chemistry of Transition Metals: Metalloporphyrins as a Case of Study.

Herein we have evidenced the formation of favorable π-hole Br⋅⋅⋅metal noncovalent interactions (NCIs) involving elements from groups 9, 11 and 12. More in detail, M (M=Co, Ni, Cu and Zn) containing porphyrins have been synthesized and their supramolecular assemblies structurally characterized by means of single crystal X-ray diffraction and Hirshfeld surface analyses, revealing the formation of directional Br⋅⋅⋅M contacts in addition to ancillary hydrogen bond and lone pair-π bonds. Computations at the PBE0-D3/def2-TZVP level of theory revealed the π-hole nature of the Br⋅⋅⋅M interaction.

Using Hybrid PDI-FeO Nanoparticles for Capturing Aliphatic Alcohols: Halogen Bonding vs. Lone Pair-π Interactions.

In this study, FeO nanoparticles (FeNPs) decorated with halogenated perylene diimides (PDIs) have been used for capturing VOCs (volatile organic compounds) through noncovalent binding. Concretely, we have used tetrachlorinated/brominated PDIs as well as a nonhalogenated PDI as a reference system. On the other hand, methanol, ethanol, propanol, and butanol were used as VOCs.