Vibrational coherences in manganese single-molecule magnets after ultrafast photoexcitation.

Magnetic recording using femtosecond laser pulses has recently been achieved in some dielectric media, showing potential for ultrafast data storage applications. Single-molecule magnets (SMMs) are metal complexes with two degenerate magnetic ground states and are promising for increasing storage density, but remain unexplored using ultrafast techniques. Here we have explored the dynamics occurring after photoexcitation of a trinuclear µ-oxo-bridged Mn(III)-based SMM, whose magnetic anisotropy is closely related to the Jahn-Teller distortion.

Tetradecanuclearity in 3d-4f chemistry: relaxation and magnetocaloric effects in [NiLn] species.

The employment of 2-amino-isobutyric acid, Haib, and 2-hydroxy-1-naphthaldehyde, Hnaphth, in Ni/Ln chemistry has led to the isolation and characterization of two new isostructural 3d-4f tetradecanuclear [NiLn] clusters (Ln = Gd, Dy), with the Dy analogue displaying temperature and frequency dependent out-of-phase signals, and the Gd analogue showing interesting magnetocaloric properties.

In search of molecules displaying ferromagnetic exchange: multiple-decker Ni and Ni complexes from the use of pyridine-2-amidoxime.

The use of pyridine-2-amidoxime (pyaoxH) in Ni chemistry has provided access to a dodecanuclear complex and a hexadecanuclear Ni cluster, namely [Ni(pyaox)(pyaoxH)(MeOH)Cl]Cl·5MeOH (1·5MeOH) and [Ni(pyaox)(pyaoxH)(MeOH)](SO)·10HO·26MeOH (2·10HO·26MeOH). Complex 1·5MeOH was isolated by the reaction of NiCl·6HO, pyaoxH and NaOMe in a 1 : 1 : 2 molar ratio in MeOH in 60% yield. Treatment of NiSO·6HO with pyaoxH and NEt in a 1 : 1 : 2 molar ratio in MeOH afforded 2·10HO·26MeOH in good yield (65%).

A hexameric [MnNa] wheel based on [MnO] sub-units.

A novel hexameric [MnNa] wheel-like aggregate consisting of [MnO] triangles is reported. It is the second highest nuclearity oxime-based Mn cluster, the largest member of the recently-developed family of molecular oligomers based on [MnO] triangles, and the only one with a wheel-like metal topology.

Structurally Flexible and Solution Stable [LnTM(OH)(L)(OCR)(MeOH)](ClO): A Playground for Magnetic Refrigeration.

The family of compounds of general formula [LnTM(OH)(L)(OCR)(MeOH)](ClO) {[GdZn(OH)(hmp)(OCPr)](ClO) (1a); [YZn(OH)(hmp)(OCPr)](ClO) (1b); [GdCu(OH)(hmp)(OCPr)](ClO) (2a); [YCu(OH)(hmp)(OCPr)](ClO) (2b); [GdCu(OH)(hep)(OCPr)](ClO) (3a); [GdCu(OH)(Hpdm)(OCBu)](ClO) (4a); [GdCu(OH)(ea)(OCMe)](ClO) (5a); [GdNi(OH)(hmp)(OCEt)(MeOH)](ClO) (6a); [YNi(OH)(hmp)(OCEt)(MeOH)](ClO) (6b); [GdCo(OH)(hmp)(OCEt)(MeOH)](ClO) (7a); [YCo(OH)(hmp)(OCEt)(MeOH)](ClO) (7b)} can be formed very simply and in high yields from the reaction of Ln(NO)·6HO and TM(ClO)·6HO and the appropriate ligand blend in a mixture of CHCl and MeOH in the presence of a suitable base. Remarkably, almost all the constituent parts, namely the lanthanide (or rare earth) ions Ln (here Ln = Gd or Y), the transition metal ions TM (here TM = Zn, Cu, Ni, Co), the bridging ligand L (Hhmp = 2-(hydroxymethyl)pyridine; Hhep = 2-(hydroxyethyl)pyridine; Hpdm = pyridine-2,6-dimethanol; Hea = 2-ethanolamine), and the carboxylates can be exchanged while maintaining the structural integrity of the molecule. NMR spectroscopy of diamagnetic complex 1b reveals the complex to be fully intact in solution with all signals from the hydroxide, ligand L, and the carboxylates equivalent on the NMR time scale, suggesting the complex possesses greater symmetry in solution than in the solid state.

Copper Keplerates: High-Symmetry Magnetic Molecules.

Keplerates are molecules that contain metal polyhedra that describe both Platonic and Archimedean solids; new copper keplerates are reported, with physical studies indicating that even where very high molecular symmetry is found, the low-temperature physics does not necessarily reflect this symmetry.

A triacontanuclear [Zn12Dy18] cluster: a ring of [Dy4] cubes.

The reaction between Dy(NO3)3·6H2O, Zn(OAc)2·4H2O, salicylaldehyde and 2-amino-isobutyric acid, in MeOH in the presence of NEt3 under solvothermal conditions, led to the isolation of the triacontanuclear mixed-metal cluster [Zn(II)12Dy(III)18(OH)30(L)12(sal)6(OAc)6(NO3)3(H2O)6](NO3)3·12MeOH·5H2O (1·12MeOH·5H2O), which displays frequency- and temperature-dependent out-of-phase magnetic susceptibility signals.

Solvothermal synthesis of enneanuclear [Cu₇(II)Ln₂(III)] clusters.

Employment of H3L (= 2-(β-naphthalideneamino)-2-hydroxymethyl-1-propanol) in mixed-metal copper-lanthanide cluster chemistry has led to the isolation of four new enneanuclear heteronuclear isostructural [Cu₇(II)Ln₂(III)] complexes. More specifically, the solvothermal reaction of Cu2(OAc)4·2H2O with H3L and the corresponding lanthanide nitrate salt in MeCN in the presence of a base, NEt3, yielded three complexes with the general formula [Cu₇(II)Ln₂(III)(L)4(HL)2(OAc)4]·2MeCN (Ln: Gd, 1·2MeCN; Tb, 2·2MeCN; Dy, 3·2MeCN), while in addition the Y(III) analogue, [Cu₇(II)Y₂(III)(L)4(HL)2(OAc)4]·2MeCN (4·2MeCN), was also synthesized in the same manner. The structure of the cluster describes two corner-sharing [Cu3Ln] cubane metallic units, each one further connected to one Cu(II) ion.

Enneanuclear [Ni6Ln3] Cages: [Ln(III)3] Triangles Capping [Ni(II)6] Trigonal Prisms Including a [Ni6Dy3] Single-Molecule Magnet.

The use of (2-(β-naphthalideneamino)-2-hydroxymethyl-1-propanol) ligand, H3L, in Ni/Ln chemistry has led to the isolation of three new isostructural [Ni(II)6Ln(III)3] metallic cages. More specifically, the reaction of Ni(ClO4)2·6H2O, the corresponding lanthanide nitrate salt, and H3L in MeCN, under solvothermal conditions in the presence of NEt3, led to the isolation of three complexes with the formulas [Ni6Gd3(OH)6(HL)6(NO3)3]·5.75MeCN·2Et2O·1.

Dodecanuclear [Mn6(III)Ln6(III)] species: synthesis, structures and characterization of magnetic relaxation phenomena.

The use of H3L (= 2-(β-naphthalideneamino)-2-hydroxymethyl-1-propanol) in mixed-metal manganese-lanthanide carboxylate cluster chemistry has led to the isolation of two new dodecametallic heteronuclear isostructural [Mn6(III)Ln6(III)] complexes (Ln = Gd, Dy), with the Dy analogue displaying temperature and frequency dependent out-of-phase signals suggesting possible single molecule magnetism behaviour.

A family of [Mn(III)₆Ln(III)₂] rod-like clusters.

Employment of H3L (= 2-(β-naphthalideneamino)-2-hydroxymethyl-1-propanol) in mixed-metal manganese-lanthanide cluster chemistry has led to the isolation of five new octametallic heteronuclear isostructural [Mn(III)6Ln(III)2] complexes. More specifically, the reaction of Mn(ClO4)2·6H2O with H3L and the corresponding lanthanide nitrate in MeCN in the presence of a base, NEt3, yielded four complexes with the general formula [Mn(III)6Ln(III)2O2(OH)2(H2O)2(HL)6(NO3)6]·6MeCN·0.5H2O (Ln: Gd, 1·6MeCN·0.

Three-leaf quantum interference clovers in a trigonal single-molecule magnet.

We report on a single-molecule magnet where the spatial arrangement of three manganese ions and their spin-orbit coupling tensor orientations result in threefold angular modulations of the magnetization tunneling rates and quantum interference patterns that mimic the form of a three-leaf clover. Although expected in all quantum tunneling of magnetization resonances for a trigonal molecular symmetry, the threefold modulation only appears at resonances for which a longitudinal magnetic field is applied (i.e.

Chiral single-chain magnet: helically stacked [Mn(III)2Cu(II)] triangles.

The one-dimensional complex [Mn(III)2Cu(II)(μ3-O)(Cl-sao)3(EtOH)2]·EtOH (Mn2Cu) was obtained by the metal replacement reaction of the trinuclear manganese complex (Et3NH)[Mn(III)3(μ3-O)Cl2(Cl-sao)3(MeOH)2(H2O)2] with [Cu(acac)2]. The Mn2Cu chain exhibits single-chain-magnet behavior with finite-size effects due to its large magnetic anisotropy.

CO2 as a reaction ingredient for the construction of metal cages: a carbonate-panelled [Gd6Cu3] tridiminished icosahedron.

A CO3(2-)-panelled [Gd(III)6Cu(II)3] cage conforming to a tridiminished icosahedron is synthesised by bubbling CO2 through a solution of Gd(III) and Cu(II) ions.

From antiferromagnetic to ferromagnetic exchange in a family of oxime-based Mn(III) dimers: a magneto-structural study.

The reaction of Mn(ClO4)2·6H2O, a derivatised phenolic oxime (R-saoH2) and the ligand tris(2-pyridylmethyl)amine (tpa) in a basic alcoholic solution leads to the formation of a family of cluster compounds of general formula [Mn(III)2O(R-sao)(tpa)2](ClO4)2 (1, R = H; 2, R = Me; 3, R = Et; 4, R = Ph). The structure is that of a simple, albeit asymmetric, dimer of two Mn(III) ions bridged through one μ-O(2-) ion and the -N-O- moiety of the phenolic oxime. Magnetometry reveals that the exchange interaction between the two Mn(III) ions in complexes 1, 3 and 4 is antiferromagnetic, but that for complex 2 is ferromagnetic.

A 1-D coordination polymer based on a Mn40 octagonal super-structure.

A 1-D coordination polymer, constructed using a combination of diols and phenolic oximes, contains a novel [Mn(9)] sub-unit, a nanosized [Mn(40)] octagonal super-structure and a [Mn(21)] repeating unit.

A flow-system array for the discovery and scale up of inorganic clusters.

The batch synthesis of inorganic clusters can be both time consuming and limited by a lack of reproducibility. Flow-system approaches, now common in organic synthesis, have not been utilized widely for the synthesis of clusters. Herein we combine an automated flow process with multiple batch crystallizations for the screening and scale up of syntheses of polyoxometalates and manganese-based single-molecule magnets.

Twisted molecular magnets.

The use of derivatised salicylaldoximes in manganese chemistry has led to the synthesis of a family of approximately fifty hexanuclear ([Mn(III)(6)]) and thirty trinuclear ([Mn(III)(3)]) Single-Molecule Magnets (SMMs). Deliberate, targeted structural distortion of the metallic core afforded family members with increasingly puckered configurations, leading to a switch in the pairwise magnetic exchange from antiferromagnetic to ferromagnetic. Examination of both the structural and magnetic data revealed a semi-quantitative magneto-structural correlation, from which the factors governing the magnetic properties could be extracted and used for predicting the properties of new family members and even more complicated structures containing analogous building blocks.

Accidentally on purpose: construction of a ferromagnetic, oxime-based [Mn(III)2] dimer.

The serendipitous self-assembly of the complex [Mn(III)(2)Zn(II)(2)(Ph-sao)(2)(Ph-saoH)(4)(hmp)(2)] (1),whose magnetic core consists solely of two symmetry equivalent Mn(iii) ions linked by two symmetry equivalent -N-O- moieties, provides a relatively simple model complex with which to study the magneto-structural relationship in oxime-bridged Mn(III) cluster compounds. Dc magnetic susceptibility measurements reveal ferromagnetic (J = +2.2 cm(-1)) exchange resulting in an S = 4 ground state.

A new family of Mn₆ SMMs using phosphinate ligands.

A new family of hexametallic [Mn(III)₆] Single-Molecule Magnets with general formula [Mn₆O₂(R-sao)₆(X)₂(MeOH)₄₋₆] (R= H, Me, Et or Ph; X = O₂PHPh or O₂P(Ph)₂) have been synthesised and characterised. The molecules are new members of the [Mn₆] family of SMMs in which the carboxylate ligands have been replaced with phenyl- and diphenylphosphinate. The magnetic cores remain largely unaltered meaning that structural distortions of the Mn-N-O-Mn torsion angles in the [Mn₃O] subunits can be used to tune the magnetic properties, switching pairwise exchange interactions from antiferromagnetic to ferromagnetic.

Ferromagnetic manganese "cubes": from PSII to single-molecule magnets.

The reaction of Mn(O₂CMe)₂·2H₂O with Me-saoH₂ (Me-saoH₂ = 2-hydroxyphenylethanone oxime) in MeCN forms the complex [Mn(III)₄(Me-sao)₄(Me-saoH)₄] (1) in good yields. Replacing Me-saoH₂ with Naphth-saoH₂ (Naphth-saoH₂ = 2-hydroxy-1-napthaldoxime) in the presence of CH₃ONa forms the complex [Mn(III)₄(Naphth-sao)₄(Naphth-saoH)₄] (2) in low yields, while the reaction between Mn(ClO₄)₂·6H₂O, Et-saoH₂ (Et-saoH₂= 2-hydroxypropiophenone oxime) and NBu₄OH in MeCN gives the complex [Mn(III)₄(Et-sao)₄(Et-saoH)₄] (3) in moderate yields. All three tetrametallic cages exclusively contain Mn(III) centres arranged in a "cube"-like topology, in which the metal centres are connected by -N-O(oximate) groups.

Enhancing U(eff) in oxime-bridged [Mn(III)6Ln(III)2] hexagonal prisms.

The first 3d-4f clusters built using derivatised salicylaldoximes (R-saoH(2)) describe unusual hexagonal prisms. Replacement of the paramagnetic Gd(III) ions with diamagnetic Ln(III) ions allows for a more thorough understanding of the magnetic properties, whilst replacement with Tb(III) doubles U(eff).

Chiral single-molecule magnets: a partial Mn(III) supertetrahedron from achiral components.

A [Mn(III)(9)] partial supertetrahedron is a Single-Molecule Magnet (SMM) with an energy barrier to magnetisation reversal of ~30 K and represents the first chiral SMM obtained from achiral starting materials.

Hexametallic manganese clusters with bulky derivatised salicylaldoximes.

The reaction of Mn(ClO(4))(2)·6H(2)O with Ph-saoH(2) (Ph-saoH(2) = 2-hydroxybenzophenone oxime) in MeCN in the presence of sodium propionate forms the complex [Mn(III)(6)O(2)(Ph-sao)(6)(prop)(2)(MeCN)(2)]·5.27MeCN (1·5.27MeCN) (prop = propionate).