Synthesis and Structure of the Bis- and Tris-Polyhedral Hybrid Carboranoclathrochelates with Functionalizing Biorelevant Substituents-The Derivatives of Propargylamine Iron(II) Clathrochelates with Terminal Triple C≡C Bond(s).

A synthetic strategy for obtaining structurally flexible hybrid iron(II) carboranoclatrochelates functionalized with biorelevant groups, based on a combination of a 1,3-dipolar cycloaddition reaction with nucleophilic substitution of an appropriate chloroclathrochelate precursor, was developed. In its first stage, a stepwise substitution of the dichloroclathrochelate precursor with amine N-nucleophiles of different natures in various solvents was performed. One of its two chlorine atoms with morpholine or diethylamine in dichloromethane gave reactive monohalogenoclathrochelate complexes functionalized with abiorelevant substituents. Further nucleophilic substitution of their remaining chlorine atoms with propargylamine in DMF led to morpholine- and diethylamine-functionalized monopropargylamine cage complexes, the molecules of which contain the single terminal C≡C bond. Their "click" 1,3-cycloaddition reactions in toluene with ortho-carborane-(1)-methylazide catalyzed by copper(II) acetate gave spacer-containing di- and tritopic iron(II) carboranoclatrochelates formed by a covalent linking between their different polyhedral(cage) fragments. The obtained complexes were characterized using elemental analysis, MALDI-TOF mass, UV-Vis, 1H, 1H{11B}, 11B, 11B{1H}, 19F{1H} and 13C{1H}-NMR spectra, and by a single crystal synchrotron X-ray diffraction experiment for the diethylamine-functionalized iron(II) carboranoclathrochelate. Its encapsulated iron(II) ion is situated almost in the center of the FeN6-coordination polyhedron possessing a geometry intermediate between a trigonal prism and a trigonal antiprism with a distortion angle φ of approximately 28°. Conformation of this hybrid molecule is strongly affected by its intramolecular dihydrogen bonding: a flexibility of the carborane-terminated ribbed substituent allowed the formation of numerous C-H…H-B intramolecular interactions. The H(C) atom of this carborane core also forms the intermolecular C-H…F-B interaction with an adjacent carboranoclathrochelate molecule. The N-H…N intermolecular interaction between the diethylamine group of one hybrid molecule and the heterocyclic five-membered 1H-[1,2,3]-triazolyl fragment of the second molecule of this type caused formation of H-bonded carboranoclathrochelate dimers in the X-rayed crystal.

Ligand Aspect Ratio as a Decisive Factor for the Self-Assembly of Coordination Cages.

It is possible to control the geometry and the composition of metallasupramolecular assemblies via the aspect ratio of their ligands. This point is demonstrated for a series of iron- and palladium-based coordination cages. Functionalized clathrochelate complexes with variable aspect ratios were used as rod-like metalloligands. A cubic Fe(II)8L12 cage was obtained from a metalloligand with an intermediate aspect ratio. By increasing the length or by decreasing the width of the ligand, the self-assembly process resulted in the clean formation of tetrahedral Fe(II)4L6 cages instead of cubic cages. In a related fashion, it was possible to control the geometry of Pd(II)-based coordination cages. A metalloligand with a large aspect ratio gave an entropically favored tetrahedral Pd(II)4L8 assembly, whereas an octahedral Pd(II)6L12 cage was formed with a ligand of the same length but with an increased width. The aspect ratio can also be used to control the composition of dynamic mixtures of Pd(II) cages. Out of two metalloligands with only marginally different aspect ratios, one gave rise to a self-sorted collection of Pd(II)4L8 and Pd(II)6L12 cages, whereas the other did not.

Cytotoxicity of electrophilic iron(II)-clathrochelates in human promyelocytic leukemia cell line.

We observed that electrophilic iron(II)-clathrochelates exhibit significant cytotoxicity in human promyelocytic leukemia cells (IC50=6.5±4.6µM), which correlates with the enhancement of intracellular oxidative stress (17-fold increase with respect to the cells treated with the solvent only). Based on in vitro studies we suggested that this effect is caused by alkylation of glutathione leading to inhibition of the cellular antioxidative system and by catalytic generation of reactive oxygen species by products of the alkylation reaction.

Synthesis, crystal polymorphism and spin crossover behavior of adamantylboron-capped cobalt(II) hexachloroclathrochelate and its transformation into the CoIIICoIICoIII-bis-macrobicyclic derivative.

Fast crystallization of the monoclathrochelate cobalt(II) intracomplex [Co(Cl2Gm)3(BAd)2] (where Cl2Gm2- is a dichloroglyoxime dianion and BAd is an adamantylboron capping group, 1), initially obtained by the direct template condensation of the corresponding chelating α-dioximate and cross-linking ligand synthons on the Co2+ ion as a matrix, from benzene or dichloromethane afforded its structural triclinic and hexagonal polymorphs. Its prolonged recrystallization from dichloromethane under air atmosphere and sunlight irradiation unexpectedly gave the crystals of the CoIIICoIICoIII-trinuclear dodecachloro-bis-clathrochelate intracomplex [[CoIII(Cl2Gm)3(BAd)]2CoII] (2), the molecule of which consists of two macrobicyclic frameworks with encapsulated low-spin (LS) Co3+ ions, which are cross-linked by a µ3-bridging Co2+ ion as a bifunctional Lewis-acidic center. The most plausible pathway of such a 1 → 2 transformation is based on the photoinitiated radical oxidation of dichloromethane with air oxygen giving the reactive species. Cobalt(II) monoclathrochelate 1 was found to undergo a temperature-induced spin crossover (SCO) both in its solutions and in the solid state. In spite of the conformational rigidity of the corresponding quasiaromatic diboron-capped tris-α-dioximate framework, the main parameters of this SCO transition (i.e., its completeness and gradual character) are strongly affected by the nature of the used solvent (in the case of its solutions) and by the structural polymorphism of its crystals (in the solid state). In the latter case, the LS state (S = 1/2) of this complex is more thermally stable and, therefore, the cobalt(II)-centered 1/2 → 3/2 SCO is more gradual than that in solutions.

A New Series of Cobalt and Iron Clathrochelates with Perfluorinated Ribbed Substituents.

The study tackles one of the challenges in developing platinum-free molecular electrocatalysts for hydrogen evolution, which is to seek for new possibilities to ensure large turnover numbers by stabilizing electrocatalytic intermediates. These species are often much more reactive than the initial electrocatalysts, and if not properly stabilized by a suitable choice of functionalizing substituents, they have a limited long-time activity. Here, we describe new iron and cobalt(II) cage complexes (clathrochelates) that in contrast to many previously reported complexes of this type do not act as electrocatalysts for hydrogen evolution. We argue that the most probable reason for this behavior is an excessive stabilization of the metal(I) species by perfluoroaryl ribbed groups, resulting in an unprecedented long-term stability of the metal(I) complexes even in acidic solutions.

Molecular design of cage iron(II) and cobalt(II,III) complexes with a second fluorine-enriched superhydrophobic shell.

Pentafluorophenylboron-capped iron and cobalt(II) hexachloroclathrochelate precursors were obtained by the one-pot template condensation of dichloroglyoxime with pentafluorophenylboronic acid on iron and cobalt(II) ions under vigorous reaction conditions in trifluoroacetic acid media. These reactive precursors easily undergo nucleophilic substitution with (per)fluoroarylthiolate anions, giving (per)fluoroarylsulfide macrobicyclic complexes with encapsulated iron and cobalt(II) ions; nucleophilic substitution of the cobalt(II) hexachloroclathrochelate precursor with a pentafluorophenylsulfide anion gave the target hexasulfide monoclathrochelate and the mixed-valence Co(III)Co(II)Co(III) bis-clathrochelate as a side product. The complexes obtained were characterized using elemental analysis, MALDI-TOF mass spectrometry, IR, UV-Vis, (57)Fe Mössbauer (for the X-rayed iron complexes), (1)H, (11)B, (13)C and (19)F NMR spectroscopies and by X-ray diffraction; their redox and electrocatalytic behaviors were studied using cyclic voltammetry and gas chromatography. As can be seen from the single-crystal X-ray diffraction data, the second superhydrophobic shell of such caged metal ions is formed by fluorine atoms of both the apical and ribbed (per)fluoroaryl peripheral groups. The main bond distances and chelate N=C-C=N angles in their molecules are similar, but rotational elongation (contraction) along the molecular C3-pseudoaxes, accompanied by changes in the geometry of the corresponding MN6-coordination polyhedra from a trigonal prism to a trigonal antiprism, allowed encapsulating Fe(2+), Co(2+) and Co(3+) ions. The nature of an encapsulated metal ion and its oxidation state affect the M-N bond lengths, and, for cobalt(ii) clathrochelate with an electronic configuration d(7) the Jahn-Teller structural effect is observed as an alternation of the Co-N distances. Pentafluorophenylboron-capped hexachloroclathrochelate precursors, giving stable catalytically active metal(I)-containing intermediates due to the electron-withdrawing effect of their six ribbed chlorine substituents, were found to show moderate electrocatalytic activity in a 2H(+)/H2 hydrogen-forming reaction. In the case of their ribbed-functionalized sulfide derivatives, the strong electron-withdrawing (per)fluoroaryl groups do not stabilize the reduced electrocatalytically active metal(i)-containing species as their mesomeric effect is absent or substantially decreased by steric hindrances between them.

First iron and cobalt(II) hexabromoclathrochelates: structural, magnetic, redox, and electrocatalytic behavior.

Template condensation of dibromoglyoxime with n-butylboronic acid on the corresponding metal ion as a matrix under vigorous reaction conditions afforded iron and cobalt(ii) hexabromoclathrochelates. The paramagnetic cobalt clathrochelate was found to be a low-spin complex at temperatures below 100 K, with a gradual increase in the effective magnetic moment at higher temperatures due to the temperature 1/2↔3/2 spin crossover and a gap caused by the structure phase transition. The multitemperature X-ray and DSC studies of this complex and its iron(ii)-containing analog also showed temperature structural transitions. The variation of an encapsulated metal ion's radius, electronic structure and spin state caused substantial differences in the geometry of its coordination polyhedron; these differences increase with the decrease in temperature due to Jahn-Teller distortion of the encapsulated cobalt(ii) ion with an electronic configuration d(7). As follows from CV and GC data, these cage iron and cobalt complexes undergo both oxidation and reduction quasireversibly, and showed an electrocatalytic activity for hydrogen production in different producing systems.

Apically linked iron(II) α-dioximate and α-oximehydrazonate bis-clathrochelates: synthesis, structure and electrocatalytic properties.

Iron(II) α-oximehydrazonate and α-dioximate bis-clathrochelates with apical hydrocarbon linkers were obtained by template condensation on an iron(II) ion followed by H(+)-catalyzed macrobicyclization of the bis-semiclathrochelate precursor with formaldehyde and triethyl orthoformate, and by transmetallation of the triethylantimony-containing clathrochelate precursor with diboron-containing bifunctional Lewis acids, respectively. The geometry of the para-phenylenediboron-capped iron(II) bis-clathrochelate studied by single-crystal X-ray diffraction is intermediate between a trigonal prism and a trigonal antiprism with a distortion angle of 20.4°; the rigidity of its C6H4 linker results in the presence of the expected three-fold pseudo-rotational B···Fe···B···B···Fe···B axis and a staggered conformation of the cyclohexane-containing chelate moieties. The cyclic voltammograms (CVs) for the oximehydrazonate bis-clathrochelates contain single one-electron (for each metallocentre, and therefore, two electrons per molecule) quasi-reversible reduction waves assigned to the redox-processes of Fe(2+/+), and no interaction is observed between the two encapsulated iron(I)-containing metallocenters; six strong electron-withdrawing ethoxy substituents in the 1,3,5-triazacyclohexane capping fragments substantially affect the potential of this reduction. The corresponding waves for the dioximate complexes are irreversible: due to the structural rigidity of the caging tris-dioximate ligands, their reduced dianionic forms are unstable on the CV time scale. The CV for the hexaethoxy bis-clathrochelate complex contains one two-electron reversible oxidation wave assigned to the metal-centered oxidation of Fe(2+/3+), whereas those for its dioximate analogs are quasi-reversible. The relative lability of the ligand cavity in binuclear oximehydrazonates causes a stabilization of both the oxidized and the reduced forms; the reduced iron(I)-containing species are highly electrocatalytically active in the hydrogen-producing 2H(+)/H2 reaction. Their higher activity as compared with that for dioximate bis-clathrochelates was explained by the higher availability of the catalytically active metallocentres for H(+) ions.