A large barrier to magnetization reversal, a signature of a good single-molecule magnet (SMM), strongly depends on the structural environment of a paramagnetic metal ion. In a crystalline state, where SMM properties are usually measured, this environment is influenced by crystal packing, which may be different for the same chemical compound, as in polymorphs. Here we show that polymorphism can dramatically change the magnetic behavior of an SMM even with a very rigid coordination geometry. For a cobalt(II) clathrochelate, it results in an increase of the effective barrier from 109 to 180 cm, the latter value being the largest one reported to date for cobalt-based SMMs. Our finding thus highlights the importance of identifying possible polymorphic phases in search of new, even more efficient SMMs.

Boron-capped hexachlorine-containing cobalt(II) clathrochelates were prepared by means of template condensation of dichloroglyoxime (Cl 2 GmH 2 ) with boron-containing Lewis acids on a cobalt(II) ion matrix. The nucleophilic substitution of the reactive chlorine atoms of these macrobicyclic tris-dioximates with thiolate anions gave the hexasulfide cobalt(II) and dodecasulfide Co III Co II Co III mono-and bis-clathrochelates. The treatment of the hexachlorine-containing cobalt(II) precursors with primary aliphatic amines afforded hexaamine cobalt(III) clathrochelates. The reduction of these precursors led to the clathrochelate [Co(Cl 2 Gm) 3 (BR) 2 ] -anions, which were isolated as the salts with bulky organic cations. The relative stability of these cobalt(I) complexes accounted for a strong electronic effect of six electron-withdrawing ribbed chlorine substituents. Superconducting quantum interference device (SQUID) magnetometry, EPR, and multi-

Compounds (299) containing 494 symmetrically independent pyridine-2,6-dicarboxylate moieties have been investigated. Among them the structures of Na(3)[Nd(Pydc)(3)].14H(2)O and Na(3)[Er(Pydc)(3)].11.5H(2)O, where H(2)Pydc is pyridine-2,6-dicarboxylic acid, were determined by single-crystal X-ray diffraction, while the others were taken from the Cambridge Structural Database. The characteristics of any complex by means of the ;method of crystallochemical analysis' are described, and the coordination types of all the Pydc ions and crystallochemical formulae of all the compounds were determined. Although the ion can act as a mono-, bi-, tri-, tetra- and pentadentate ligand, 96% of Pydc ions are coordinated to the central A atom in the tridentate-chelating mode. The dependence of the denticity and geometry of pyridine-2,6-dicarboxylate, as well as of the composition of Pydc-containing complexes, was studied as a function of the nature of the A atom, the molar ratio Pydc:A and the presence of neutral or acidic ligands in the reaction mixture.

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.

Transition-metal complexes are rarely considered as paramagnetic tags for NMR spectroscopy due to them generally having relatively low magnetic anisotropy. Here we report cobalt(II) cage complexes with the largest (among the transition-metal complexes) axial anisotropy of magnetic susceptibility, reaching as high as 12.6 × 10(-32) m(3) at room temperature. This remarkable anisotropy, which results from an unusual trigonal prismatic geometry of the complexes and translates into large negative value of the zero-field splitting energy, is high enough to promote reliable paramagnetic pseudocontact shifts at the distance beyond 2 nm. Our finding paves the way toward the applications of cobalt(II) clathrochelates as future paramagnetic tags. Given the incredible stability and functionalization versatility of clathrochelates, the fine-tuning of the caging ligand may lead to new chemically stable mononuclear single-molecule magnets, for which magnetic anisotropy is of importance.

Chloride ion-aided one-pot template self-assembly of a mixed pyrazoloxime ligand with phenylboronic acid on a corresponding metal(II) ion as a matrix afforded the first boron-capped zinc, cobalt, iron, and manganese pseudoclathrochelate tris-pyrazoloximates. The presence of a pseudocross-linking hydrogen-bonded chloride ion is critical for their formation, as the same chloride-capped complexes were isolated even in the presence of large excesses of bromide and iodide ions. As revealed by X-ray diffraction, all complexes are capped with a chloride ion via three N-H···Cl hydrogen bonds that stabilize their pseudomacrobicyclic frameworks. The MN6 coordination polyhedra possess a distorted trigonal prismatic geometry, with the distortion angles φ between their nonequivalent N3 bases of approximately 0°. Temperature dependences of the effective magnetic moment for the paramagnetic complexes showed the encapsulated metal(II) ions to be in a high-spin state in the temperature range of 2-300 K. In the case of the iron(II) pseudoclathrochelate, density functional theory (DFT) and time-dependent DFT calculations were used to assess its spin state as well as the (57)Fe Mössbauer and UV-vis-NIR parameters. Cyclic voltammetry studies performed for these pseudomacrobicyclic complexes showed them to undergo irreversible or quasi-reversible metal-localized oxidations and reductions. As no changes are observed in the presence of a substantial excess of bromide ion, no anion-exchange reaction occurs, and thus the pseudoclathrochelates have a high affinity toward chloride anions in solution.

The reaction of cis-blocked, square-planar M complexes with tetratopic N-donor ligands is known to give metallasupramolecular assemblies of the formula ML. These assemblies typically adopt barrel-like structures, with the ligands paneling the sides of the barrels. However, alternative structures are possible, as demonstrated by the recent discovery of a PtL cage with unusual gyrobifastigium-like geometry. To date, the factors that govern the assembly of ML complexes are not well understood. Herein, we provide a geometric analysis of ML complexes, and we discuss how size and geometry of the ligand is expected to influence the self-assembly process. The theoretical analysis is complemented by experimental studies using different cis-blocked Pt complexes and metalloligands with four divergent pyridyl groups. Mononuclear metalloligands gave mainly assemblies of type PtL, which adopt barrel- or gyrobifastigium-like structures. Larger assemblies can also form, as evidenced by the crystallographic characterization of a PtL complex and a PtL complex. The former adopts a pentagonal barrel structure, whereas the latter displays a barrel structure with a distorted square orthobicupola geometry. The PtL complex has a molecular weight of more than 23 kDa and a diameter of 4.5 nm, making it the largest, structurally characterized ML complex described to date. A dinuclear metalloligand was employed for the targeted synthesis of pentagonal PtL barrels, which are formed in nearly quantitative yields.

Three types of unusual cagelike copper(II) methylsilsesquioxanes, namely, nona- [(MeSiO)(CuO)] 1, hexa- [(MeSiO)(HO)(CuO)(CHN)(MeSiO)(HO)(CHCOO)(CuO)(CHN)] 2, [(MeSiO)(CuO)(MeO)(CHN)] 3, and trinuclear [(MeSiO)(CuO)(CHN)] 4, were obtained in 44%, 27%, 20%, and 16% yields, respectively. Nuclearity and structural fashion of products was controlled by the choice of solvent system and ligand, specifically assisting the assembling of cage. Structures of 1-4 were determined by single-crystal X-ray diffraction analysis. Compounds 1 and 4 are the first cage metallasilsesquioxanes, containing nine and three Cu ions, respectively. Product 1 is the first observation of nonanuclear metallasilsesquioxane ever. Unique architecture of 4 represents early unknown type of molecular geometry, based on two condensed pentamembered siloxane cycles. Topological analysis of metal clusters in products 1-4 is provided. Complex 1 efficiently catalyzes oxidation of alcohols with tert-butylhydroperoxide TBHP to ketones or alkanes with HO to alkyl hydroperoxides in acetonitrile.