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The versatile coordination chemistry of (2Z,N’E)-N′-(4-oxothiazolidin-2-ylidene)picolinohydrazonamide (HAmDHotaz) facilitated the synthesis of new complexes with different silver(I) salts. This paper describes the synthesis and characterization, through elemental analysis and spectroscopic techniques (when solubility permits), of a series of compounds that illustrate the coordinative and structural diversity achievable with the HAmDHotaz ligand. Five silver clusters containing the [Ag8(AmDHotaz)4]4+nucleus were structurally analyzed by single-crystal X-ray diffraction and were found to exhibit solvomorphism. The compositions of these are [Ag8(AmDHotaz)4(NO3)3(MeOH)(H2O)](NO3)·MeOH·7.5H2O (1), {[Ag8(AmDHotaz)4(NO3)3(H2O)2](NO3)·9.5(H2O)}n(2), {[Ag8(AmDHotaz)4(NO3)3(H2O)2](NO3)·11.5(H2O)}n(2a), {[Ag8(AmDHotaz)4(NO3)2(H2O)2](NO3)(OH)·6H2O}n(3), and {[Ag8(AmDHotaz)4(NO3)2(H2O)](NO3)(OH)·4.5H2O}n(3a). Argentophilic interactions are present in each of the octanuclear structures, where Ag···Ag distances range from 2.828(2) to 2.986(1) Å. These distances are influenced by crystal packing, determined by the counterion and solvent molecules in the structure. In the solvatomorphs, solvent molecules were observed to be disordered. Various hydrogen-bonding interactions, such as N–H···O–N, O–H···O, N–H···O═C, C–H···O–N, and π–π stacking interactions, contribute to the crystal packing. The influence of these weak interactions on the crystal packing was further analyzed using DFT calculations and Bader’s theory of atoms-in-molecules, with a focus on argentophilic interactions and Ag···S interactions.

Four Pt(II)(N^N^N) compounds featuring DMSO coordination at the fourth position were synthesized. Ligands varied in terms of pyridyl central ring (hydrogen/chlorine substituent) and lateral rings (triazoles with CF3substitution or tetrazoles). Coordination to pyridine yielded tetra-nitrogen coordinated Pt(II) complexes or Pt-functionalized polymers using commercial 4-pyridyl polyvinyl (PV) or dimethylaminopyridine. Luminescence behaviors exhibited remarkable environmental dependence. While some of the molecular compounds (tetrazole derivatives) in solid state displayed quenched luminescence, all the polymers exhibited 3MMLCT emission around 600 nm. Conversely, monomer emission was evident on poly(methyl methacrylate) or polystyrene matrices. DFT calculations were used to analyze the aggregation of the complexes both at the molecular level and coordinated to the PV polymer and their influence on the HOMO–LUMO gaps.

In this study, we provide crystallographic (Protein Data Bank (PDB) inspection) and theoretical (RI-MP2/def2-TZVP//PBE0-D3/def2-SVP level of theory) evidence of the involvement of nucleobases in Regium−π bonds (RgBs). This noncovalent interaction involves an electrophilic site located on an element of group 11 (Cu, Ag, and Au) and an electron-rich species (lone pair, LP donor, or π-system). Concretely, an initial PDB search revealed several examples where RgBs were undertaken involving DNA bases and Cu(II), Ag(I), and Au(I/III) ions. While coordination positions (mainly at the N atoms of the base) are well known, the noncovalent binding force between these counterparts has been scarcely studied in the literature. In this regard, computational models shed light on the strength and directionality properties of the interaction, which was also further characterized from a charge-density perspective using Bader’s “atoms in molecules” (AIM) theory, noncovalent interaction plot (NCIplot) visual index, and natural bonding orbital (NBO) analyses. As far as our knowledge extends, this is the first time that RgBs in metal–DNA complexes are systematically analyzed, and we believe the results might be useful for scientists working in the field of nucleic acid engineering and chemical biology as well as to increase the visibility of the interaction among the biological community.

In this study, the stability, directionality, and physical nature of Spodium bonds (SpBs, an attractive noncovalent force involving elements from group 12 and Lewis bases) between methylmercury (MeHg) and ethylmercury (EtHg) and amino acids (AAs) have been analyzed from both a structural (X-ray analysis) and theoretical (RI-MP2/def2-TZVP level of theory) point of view. More in detail, an inspection of the Protein Data Bank (PDB) reported evidence of noncovalent contacts between MeHg and EtHg molecules and electron-rich atoms (e.g., O atoms belonging to the protein backbone and S atoms from MET residues or the π-systems of aromatic AAs such as TYR or TRP). These results were rationalized through a computational study using MeHg coordinated to a thiolate group as a theoretical model and several neutral and charged electron-rich molecules (e.g., benzene, formamide, or chloride). The physical nature of the interaction was analyzed from electrostatics and orbital perspectives by performing molecular electrostatic potential (MEP) and natural bonding orbital (NBO) analyses. Lastly, the noncovalent interactions plot (NCIplot) technique was used to provide a qualitative view of the strength of the Hg SpBs and compare them to other ancillary interactions present in these systems as well as to shed light on the extension of the interaction in real space. We believe that the results derived from our study will be useful to those scientists devoted to protein engineering and bioinorganic chemistry as well as to expanding the current knowledge of SpBs among the chemical biology community.