An [FeIII30] molecular metal oxide.

Dissolution of FeBr in a mixture of acetonitrile and 3,4-lutidine in the presence of an amine results in the formation of an [Fe] molecular metal oxide containing alternating layers of tetrahedral and octahedral Fe ions. Mass spectrometry suggests the cluster is formed quickly and remains stable in solution, while magnetic measurements and DFT calculations reveal competing antiferromagnetic exchange interactions.

[(VO)MII5] (M = Ni, Co) Anderson wheels.

Heterometallic Anderson wheels of formula [(VO)MII5(hmp)Cl](ClO)·2MeOH (M = Ni, 1; Co, 2) have been synthesised from the solvothermal reaction of M(ClO)·6HO and VCl with hmpH (2-(hydroxymethyl)pyridine). The metallic skeleton describes a centred hexagon, with the two vanadyl ions sitting on opposing sides of the outer ring. Magnetic susceptibility and magnetisation measurements indicate the presence of both ferromagnetic and antiferromagnetic exchange interactions.

An [Fe ] Molecular Metal Oxide.

The dissolution of anhydrous iron bromide in a mixture of pyridine and acetonitrile, in the presence of an organic amine, results in the formation of an [Fe ] metal oxide molecule, structurally characterised by alternate layers of tetrahedral and octahedral Fe ions connected by oxide and hydroxide ions. The outer shell of the complex is capped by a combination of pyridine molecules and bromide ions. Magnetic data, measured at temperatures as low as 0.

A Ferromagnetically Coupled, Bell-Shaped [NiGd] Cage.

Reaction between NiCl·6HO, 2-hydroxy-4-methyl-6-phenyl-pyridine-3-amidoxime (HL), benzoic acid, and M(NO)·6HO (M = Gd, Y) in MeCN under basic conditions yields the complexes [NiGd(PhCOO)(HL)(HL)(OH)(NO)]Cl·13.6MeCN·HO (·13.6MeCN·HO) and [NiY(PhCOO)(HL)(HL)(OH)(NO)(HO)]0.

Site-Specific Metal Chelation Facilitates the Unveiling of Hidden Coordination Sites in an Fe/Fe-Seamed Pyrogallol[4]arene Nanocapsule.

Under suitable conditions, C-alkylpyrogallol[4]arenes (PgCs) arrange into spherical metal-organic nanocapsules (MONCs) upon coordination to appropriate metal ions. Herein we present the synthesis and structural characterization of a novel Fe/Fe-seamed MONC, as well as studies related to its electrochemical and magnetic behaviors. Unlike other MONCs that are assembled through 24 metal ions, this nanocapsule comprises 32 Fe ions, uncovering 8 additional coordination sites situated between the constituent PgC subunits.

Cages on a plane: a structural matrix for molecular 'sheets'.

A family of heterometallic Anderson-type 'wheels' of general formula [MM(hmp)] (M = Cr or Al and M = Ni or Zn, Hhmp = 2-pyridinemethanol) has been extended to include M = Cr or Al and M = Co, Fe, Mn or Cu, affording five new species of formulae [CrCo(hmp)](ClO) (1), [CrFe(hmp)](ClO) (2), [CrMn(hmp)](ClO) (3), [CrCu(hmp)](ClO)(NO) (4) and [AlCo(hmp)](ClO) (5). As per previous family members, the metallic skeleton common to the cations of 1-5 describes a centred hexagon with the two M sites disordered around the outer wheel, with the exception of compound 4 where the Cu sites are localised. A structurally related, but enlarged planar disc possessing a [MM] hexagon capped on each edge by a Cu ion can be formed, but only when M = Al and M = Cu.

Oxidation State Distributions Provide Insight into Parameters Directing the Assembly of Metal-Organic Nanocapsules.

Two structurally analogous Mn-seamed C-alkylpyrogallol[4]arene (PgC )-based metal-organic nanocapsules (MONCs) have been synthesized under similar reaction conditions and characterized by crystallographic, electrochemical, and magnetic susceptibility techniques. Both MONCs contain 24 Mn centers, but, somewhat surprisingly, marked differences in oxidation state distribution are observed upon analysis. One MONC contains exclusively Mn ions, while the other is a mixed-valence Mn/ Mn assembly.

A simple methodology for constructing ferromagnetically coupled Cr(iii) compounds.

A large family of chromium(iii) dimers has been synthesised and magneto-structurally characterised using a combination of carboxylate and diethanolamine type ligands. The compounds have the general formula [Cr2(R1-deaH)2(O2CR2)Cl2]Cl where R1 = Me and R2 = H (1), Me (2), CMe3 (3), Ph (4), 3,5-(Cl)2Ph (5), (Me)5Ph (6), R1 = Et and R2 = H (7), Ph (8). The compound [Cr2(Me-deaH)2Cl4] (9) was synthesised in order to study the effect of removing/adding the carboxylate bridge on the observed magnetic behaviour.

In situ redox reactions facilitate the assembly of a mixed-valence metal-organic nanocapsule.

C-alkylpyrogallol[4]arenes (PgCs) have been studied for their ability to form metal-organic nanocapsules (MONCs) through coordination to appropriate metal ions. Here we present the synthesis and characterization of an Mn/Mn-seamed MONC in addition to its electrochemical and magnetic behavior. This MONC assembles from 24 manganese ions and 6 PgCs, while an additional metal ion is located on the capsule interior, anchored through the introduction of bridging nitrite ions.

Order in disorder: solution and solid-state studies of [MM] wheels (M = Cr, Al; M = Ni, Zn).

A family of heterometallic Anderson-type 'wheels' of general formula [MIII2MII5(hmp)12](ClO4)4 (where MIII = Cr or Al and MII = Ni or Zn giving [Cr2Ni5] (1), [Cr2Zn5] (2), [Al2Ni5] (3) and [Al2Zn5] (4); hmpH = 2-pyridinemethanol) have been synthesised solvothermally. The metallic skeleton common to all structures describes a centred hexagon with the MIII sites disordered around the outer wheel. The structural disorder has been characterised via single crystal X-ray crystallography, 1-3D 1H and 13C solution-state NMR spectroscopy of the diamagnetic analogue (4), and solid-state 27Al MAS NMR spectroscopy of compounds (3) and (4).

Magneto-structural correlations in a family of di-alkoxo bridged chromium dimers.

A series of di-alkoxo bridged Cr(iii) dimers have been synthesised using pyridine alcohol ligands. The structures fall into four general categories and are of formula: [Cr(OMe)(pic)]·½MeOH·½EtO (1), [Cr(hmp)(pic)X] (where X = Cl (2), Br (3)), [Cr(L)Cl(A)]·2S (where L = hmp, A = HO and S = EtO (4); L = hmp, A = pyridine and S = pyridine (5); L = hmp, A = 4-picoline and no S (6); L = hep, A = HO and S = MeCN (7)), and [Cr(hmp)(hmpH)Cl]·MeCN (8). Direct current (DC) magnetic susceptibility measurements show relatively weak antiferromagnetic exchange interactions between the Cr(iii) centres with J values <|15| cm in all of the complexes measured.