Comparative Extraction of Aluminum Group Metals Using Acetic Acid Derivatives with Three Different-Sized Frameworks for Coordination

We prepared acetic acid derivatives using three different frameworks, calix[4]arene, alkenyltrimethylol, and trihydroxytriphenylmethane, which differ in the number and size of their coordination sites. We further investigated the extraction properties for aluminum group metal ions. All three extraction reagents exhibited increased extraction compared with the corresponding monomeric compounds, owing to structural effects. The extraction reaction and extraction equilibrium constants were determined using a slope analysis. Their extraction abilities, separation efficiencies, and potential coordination modes are discussed using the extraction equilibrium constants, half-pH values, and spectroscopic data. The calix[4]arene and trihydroxytriphenylmethane derivatives demonstrated allosteric co-extraction of indium ions (In3+) with an unexpected stoichiometry of 1:2.

Stereochemistry and chiroptical properties of bimetallic single helicates of hexapyrrole-α, ω-dicarbaldimines with high diastereoselectivity

Bimetallic complexes of hexapyrrole-[Formula: see text],[Formula: see text]-dicarbaldimines consisting of a pair of four-coordinate metal sites adopt a helical closed [Formula: see text]-symmetric form or sigmoidal open forms depending on whether the 2,2[Formula: see text]-bipyrrole subunit at the center of the hexapyrrole chain takes cis- or trans-conformation. X-ray crystallography of a bisNi complex having N-[([Formula: see text]-1-cyclohexylethyl]carbaldimine units at both ends of the hexapyrrole chain revealed a non-symmetric heterohelical open form where the metal coordination sites of opposite helical sense sit on opposite sides of the central 2,2[Formula: see text]-bipyrrole subunit. BisPd complexes preferred a closed [Formula: see text] form and a steric bulk at the 3,3[Formula: see text]-position of the 2,2[Formula: see text]-bipyrrole subunit improved the helical sense bias. A bisPd complex with N-[([Formula: see text]-1-cyclohexylethyl]carbaldimine units adopts a helical closed [Formula: see text] form exclusively with full bias for a [Formula: see text]-helical sense. These bimetallic single stranded helicates were reversibly oxidized to [Formula: see text]-cation radicals at 0.1[Formula: see text]0.3 V vs. a ferrocene/ferrocenium couple and spectroelectrochemistry revealed remarkable absorption and CD spectral changes in the Vis-NIR region.

Synthesis and Spectroscopic Investigations of Schiff Base Ligand and Its Bimetallic Ag(I) Complex as DNA and BSA Binders

Generation of well-defined potential metallotherapeutics for cancer treatment, one of the most population-threatening diseases, is challenging and an active area of modern research in view of their unique properties and thus multiple possible pathways of action in cells. Specifically, Schiff base ligands were recognized as very promising building blocks for the construction of stable and active complexes of numerous geometries and topologies. Incorporation of Ag(I) ions allows for the formation of flat complexes with potential unoccupied coordination sites, thus giving rise to specific interactions between the metallotherapeutic and biomolecule of interest. Herein, we present the design, synthesis and characterization of new Schiff base ligand L and its Ag(I) bimetallic complex [Ag2L2]2+ with two planar moieties formed around the metal ions and connected through cyclohexane rings, confirmed by X-ray measurements. The compounds were described in context of their potential use as anticancer drugs through DNA and BSA binding pathways by several spectroscopic methods (CD, UV-Vis, fluorescence). We revealed that both, L and [Ag2L2]2+, interact with similar affinity with CT-DNA (Kb~106 M−1), while they differ in the type and strength of interactions with the model albumin–BSA. [Ag2L2]2+ binds BSA in both a dynamic and static manner with the Ksv = 8.8 × 104 M−1 in the Trp-134 and Trp-213 sites, whereas L interacts with BSA only dynamically (KSV = 2.4 × 104 M−1). This found further confirmation in the CD studies which revealed a reduction in α-helix content in the albumin of 16% in presence of [Ag2L2]2+.

Core Modulation of Porphyrins for Chemical Sensing

The inner core system of metal-free (‘free base’) porphyrins has continually served as a ligand for various metal ions, but it was only recently studied in organocatalysis due its highly tunable basicity. Highly conjugated porphyrin systems offer spectrophotometric sensitivity toward geometrical and/or electronic changes and, thus, utilizing the porphyrin core for the selective detection of substrates in solution offers significant potential for a multitude of applications. However, solvation and dilution drastically affect weak interactions by dispersing the binding agent to its surroundings. Thus, the spectroscopic detection of N–H···X-type binding in porphyrin solutions is almost impossible without especially designing the binding pocket. Here, we present the first report on the spectroscopic detection of N–H···X-type interplay in porphyrins formed by weak interactions. Protonated 2,3,7,8,12,13,17,18-octaethyl-5,10,15,20-tetrakis(2-aminophenyl) porphyrin contains coordination sites for the selective binding of charge-bearing analytes, revealing characteristic spectroscopic responses. While electronic absorption spectroscopy proved to be a particularly useful tool for the detection of porphyrin–analyte interactions in the supramolecular complexes, X-ray crystallography helped to pinpoint the orientation, flexibility, and encapsulation of substrates in the corresponding atropisomers. This charge-assisted complexation of analytes in the anion-selective porphyrin inner core system is ideal for the study of atropisomers using high-resolution NMR, since it reduces the proton exchange rate, generating static proton signals. Therefore, we were able to characterize all four rotamers of the nonplanar 2,3,7,8,12,13,17,18-octaethyl-5,10,15,20-tetrakis(2-aminophenyl) porphyrin by performing 1D and 2D NMR spectroscopic analyses of host-guest systems consisting of benzenesulfonic acid (BSA) and each porphyrin atropisomer. Lastly, a detailed assignment of the symmetry operations that are unique to porphyrin atropisomers allowed us to accurately identify the rotamers using NMR techniques only. Overall, the N–H···X-type interplay in porphyrins formed by weak interactions that form restricted H-bonding complexes is shown to be the key to unravelling the atropisomeric enigma.

[(1,2,5,6-η)-Cycloocta-1,5-diene](1-ethyl-3-isopropyl-1,3-imidazol-2-ylidene)(triphenylphosphane)rhodium(I) tetrafluoridoborate

A new N-heterocyclic cationic rhodium(I) complex with a tetrafluoridoborate counter-anion, [Rh(C8H14N2)(C8H12)(C18H15P)]BF4, has been prepared and structurally characterized. The cationic complex exhibits a distorted square-planar environment around the rhodium(I) ion. Two connections are made from rhodium(I) to the carbon atom of an N-heterocylic carbene ligand and to the phosphorus atom of a triphenylphosphane ligand. The remaining two coordination sites are made via a bidentate interaction from the two olefinic bonds of cyclooctadiene to the rhodium(I) ion. The compound includes an out-sphere tetrafluoridoborate counter-anion. Within the crystal of the compound exist several weak intermolecular C—H...F interactions.

Tris-{Hydridotris(1-pyrazolyl)borato}lanthanide Complexes: Synthesis, Spectroscopy, Crystal Structure and Bonding Properties

Complexes of trivalent lanthanides (Ln) with the hydridotris(1-pyrazolyl)borato (Tp) ligand Ln[η3-HB(N2C3H3)3]3 (LnTp3) were subjected to a joint experimental–theoretical analysis. X-ray diffraction experiments have been performed on CeTp3, NdTp3, SmTp3, GdTp3, and TbTp3 in the nine-fold coordination and on DyTp3, HoTp3, ErTp3, TmTp3, YbTp3, and LuTp3 in the eight-fold coordination form. Density functional theory (DFT) calculations were carried out for all 15 LnTp3 complexes. They extended the X-ray diffraction data available on the LnTp3 compounds and facilitated a straightforward interpretation of trends in the structural parameters. As a result of the joint analysis, significant steric strain in the equatorial coordination sites of the nine-coordinate structures was recognized. Trends in the bonding properties were elucidated by energy decomposition and quantum theory of atoms in molecules (QTAIM) analysis of the electron density distribution. These results revealed the major electrostatic character of the Ln…Tp bonding and fine variation of charge transfer effects across the Ln row.