Synthesis and characterization of two self-assembled [CuGd] and [CuDy] complexes exhibiting the magnetocaloric effect, slow relaxation of magnetization, and anticancer activity.

Two new paths for coordination driven self-assembly reactions under the binding support of 2-((1-hydroxy-2-methylpropan-2-ylimino)methyl)-6-methoxyphenol (HL) have been discovered from the reactions of Cu(ClO)·6HO, NEt and GdCl/DyCl·6HO in MeOH/CHCl (2 : 1) medium. A similar synthetic protocol is useful to provide two different types of self-aggregated molecular clusters [CuGd(L)(HL)(μ-Cl)(μ-OH)(OH)]ClO·4HO (1) and [CuDy(L)(HL)(μ-Cl)(μ-OH)(ClO)(HO)](ClO)·2NHEtCl·21HO (2). The adopted reaction procedure established the importance of the HO and Cl ions in the mineral-like growth of the complexes, derived from solvents and metal ion salts.

From tetranuclear to pentanuclear [Co-Ln] (Ln = Gd, Tb, Dy, Ho) complexes across the lanthanide series: effect of varying sequence of ligand addition.

Two new families of cobalt(ii/iii)-lanthanide(iii) coordination aggregates have been reported: tetranuclear [LnCoL(N-BuDEA)(OCCMe)(HO)]·(MeOH)·(HO) (Ln = Gd, 1; Tb, 2; Dy, 3; n = 2, m = 10 for 1 and 2; n = 6, m = 2 for 3) and pentanuclear LnCoCoL(N-BuDEA)(OCCMe)(MeOH) (Ln = Dy, 4; Ho, 5) formed from the reaction of two aggregation assisting ligands HL (o-vanillin oxime) and N-BuDEAH (N-butyldiethanolamine). A change in preference from a lower to higher nuclearity structure was observed on going across the lanthanide series brought about by the variation in the size of the Ln ions. An interesting observation was made for the varying sequence of addition of the ligands into the reaction medium paving the way to access both structural types for Ln = Dy.

Exploiting host-guest chemistry to manipulate magnetic interactions in metallosupramolecular ML tetrahedral cages.

Reaction of Ni(OTf) with the bisbidentate quaterpyridine ligand results in the self-assembly of a tetrahedral, paramagnetic cage [Ni ]. By selectively exchanging the bound triflate from [OTf⊂Ni ](OTf) (), we have been able to prepare a series of host-guest complexes that feature an encapsulated paramagnetic tetrahalometallate ion inside this paramagnetic host giving [MX⊂Ni ](OTf), where MX = MnCl (), CoCl (), CoBr (), NiCl (), and CuBr () or [MX⊂Ni ](OTf), where MX = FeCl () and FeBr (). Triflate-to-tetrahalometallate exchange occurs in solution and can also be accomplished through single-crystal-to-single-crystal transformations.

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.