Atomic Scale Evidence of the Switching Mechanism in a Photomagnetic CoFe Dinuclear Prussian Blue Analogue.

Molecular complexes based on Prussian Blue analogues have recently attracted considerable interest for their unique bistable properties combined to ultimately reduced dimensions. Here, we investigate the first dinuclear FeCo complex exhibiting both thermal and photomagnetic bistability in the solid state. Through an experimental and theoretical approach combining local techniques-X-ray absorption spectroscopy (XAS), X-ray magnetic circular dichroism (XMCD), and ligand field multiplet calculations-we were able to evidence the changes occurring at the atomic scale in the electronic and magnetic properties. The spectroscopic studies were able to fully support at the atomic level the following conclusions: (i) the 300 K phase and the light-induced excited state at 4 K are both built from FeLSIII-CoHSII paramagnetic pairs with no apparent reorganization of the local structure, (ii) the 100 K phase is composed of FeLSII-CoLSIII diamagnetic pairs, and (iii) the light-induced excited state is fully relaxed at an average temperature of ≈50 K. In the paramagnetic phase at 2 K, XAS and XMCD reveal that both Fe and Co ions exhibit a rather large orbital magnetic moment (0.65 µB and 0.46 µB, respectively, under an external magnetic induction of 6.5 T), but it was not possible to detect a magnetic interaction between spin centers above 2 K.

Structural Diversities in Heterometallic Mn-Ca Cluster Chemistry from the Use of Salicylhydroxamic Acid: {MnIII4Ca2}, {MnII/III6Ca2}, {MnIII/IV8Ca}, and {MnIII8Ca2} Complexes with Relevance to Both High- and Low-Valent States of the Oxygen-Evolving Complex.

One-pot reactions between the [Mn3O(O2CPh)6(py)x]+/0 triangular precursors and either CaBr2·xH2O or CaCl2·6H2O, in the presence of salicylhydroxamic acid (shaH2), have afforded the heterometallic complexes [MnIII4Ca2(O2CPh)4(shi)4(H2O)3(Me2CO)] (1) and (pyH)[MnII2MnIII4Ca2Cl2(O2CPh)7(shi)4(py)4] (2), respectively, in good yields. Further reactions but using a more flexible synthetic scheme comprising the Mn(NO3)2·4H2O/Ca(NO3)2·4H2O and Mn(O2CPh)2·2H2O/Ca(ClO4)2·4H2O "metal blends" and shaH2, in the presence of external base NEt3, led to the new complexes (NHEt3)2[MnIII4MnIV4Ca(OEt)2(shi)10(EtOH)2] (3) and (NHEt3)4[MnIII8Ca2(CO3)4(shi)8] (4), respectively. In all reported compounds, the anion of the tetradentate (N,O,O,O)-chelating/bridging ligand salicylhydroxime (shi3-), resulting from the in situ metal-ion-assisted amide-iminol tautomerism of shaH2, was found to bridge both Mn and Ca atoms. Complexes 1-4 exhibit a variety of different structures, metal stoichiometries, and Mn oxidation-state descriptions; 1 possesses an overall octahedral metal arrangement, 2 can be described as a Mn4Ca2 octahedron bound to an additional Mn2 unit, 3 consists of a Mn8 "ring" surrounding a CaII atom, and 4 adopts a rectangular cuboidal motif of eight Mn atoms accommodating two CaII atoms. Solid-state direct-current magnetic susceptibility studies revealed the presence of predominant antiferromagnetic exchange interactions between the Mn centers, leading to S = 0 spin ground-state values for all complexes. From a bioinorganic chemistry perspective, the reported compounds may demonstrate some relevance to both high-valent scheme (3) and lower-oxidation-level species (1, 2, and 4) of the catalytic cycle of the oxygen-evolving complex.

Switchable Fe/Co Prussian blue networks and molecular analogues.

With the long term objective to build the next generation of devices from the molecular scale, scientists have explored extensively in the past two decades the Prussian blue derivatives and their remarkable physico-chemical properties. In particular, the exquisite Fe/Co system displays tuneable optical and magnetic behaviours associated with thermally and photo-induced metal-to-metal electron transfer processes. Recently, numerous research groups have been involved in the transfer of these electronic properties to new Fe/Co coordination networks of lower dimensionality as well as soluble molecular analogues in order to facilitate their manipulation and integration into devices. In this review, the most representative examples of tridimensional Fe/Co Prussian blue compounds are described, focusing on the techniques used to understand their photomagnetic properties. Subsequently, the different strategies employed toward the design of new low dimensional Prussian blue analogues based on a rational molecular building block approach are discussed emphasizing the advantages of these functional molecular systems.

Large Orbital Magnetic Moment Measured in the [TpFe(III)(CN)3](-) Precursor of Photomagnetic Molecular Prussian Blue Analogues.

Photomagnetism in three-dimensional Co/Fe Prussian blue analogues is a complex phenomenon, whose detailed mechanism is not yet fully understood. Recently, researchers have been able to prepare molecular fragments of these networks using a building block synthetic approach from mononuclear precursors. The main objective in this strategy is to isolate the smallest units that show an intramolecular electron transfer to have a better understanding of the electronic processes. A prior requirement to the development of this kind of system is to understand to what extent electronic and magnetic properties are inherited from the corresponding precursors. In this work, we investigate the electronic and magnetic properties of the FeTp precursor (N(C4H9)4)[TpFe(III)(CN)3], (Tp being tris-pyrazolyl borate) of a recently reported binuclear cyanido-bridged Fe/Co complex. X-ray absorption spectroscopy and X-ray magnetic circular dichroism measurements at the Fe L2,3 edges (2p → 3d) supported by ligand field multiplet calculations have allowed to determine the spin and orbit magnetic moments. Inaccuracy of the spin sum rule in the case of low-spin Fe(III) ion was demonstrated. An exceptionally large value of the orbital magnetic moment is found (0.9 µB at T = 2 K and B = 6.5 T) that is likely to play an important role in the magnetic and photomagnetic properties of molecular Fe/Co Prussian blue analogues.

Metal-to-metal electron transfer in Co/Fe Prussian Blue molecular analogues: the ultimate miniaturization.

Co/Fe Prussian Blue analogues are known to display both thermally and light induced electron transfer attributed to the switching between diamagnetic {Fe(II)LS(µ-CN)Co(III)LS} and paramagnetic {Fe(III)LS(µ-CN)Co(II)HS} pairs (LS = low spin; HS = high spin). In this work, a dinuclear cyanido-bridged Co/Fe complex, the smallest {Fe(µ-CN)Co} moiety at the origin of the remarkable physical properties of these systems, has been designed by a rational building-block approach. Combined structural, spectroscopic, magnetic and photomagnetic studies reveal that a metal-to-metal electron transfer that can be triggered in solid state by light, temperature and solvent contents, is observed for the first time in a dinuclear complex.

2-Pyrrolyloximes in high-nuclearity transition-metal cluster chemistry: Fe10 and Fe12.

The employment of 2-pyrrolyloximes in high-nuclearity transition-metal cluster chemistry has provided access to unprecedented decanuclear and dodecanuclear Fe(III) cagelike clusters bearing the anion of pyrrole-2-carboxaldehyde oxime (praoH(2)), the simplest member of this new family of ligands; the identity of the products depends on the nature of the counteranion present in the starting materials.

First palladium(II) and platinum(II) complexes from employment of 2,6-diacetylpyridine dioxime: synthesis, structural and spectroscopic characterization, and biological evaluation.

Employment of the monoanion of 2,6-diacetylpyridine dioxime (dapdoH(2)) as a tridentate chelate in palladium(II) and platinum(II) chemistry is reported. The syntheses, crystal structures, spectroscopic and physicochemical characterization, and biological evaluation are described of [PdCl(dapdoH)] (1) and [PtCl(dapdoH)] (2). Reaction of PdCl(2) with 2 equivs of dapdoH(2) in MeOH under reflux gave 1, whereas the same reaction with PtCl(2) in place of PdCl(2) gave 2 in comparable yields (70-80%). The divalent metal center in both compounds is coordinated by a terminal chloro group and a N,N',N"-tridentate chelating (η(3)) dapdoH(-) ligand. Thus, each metal ion is four coordinate with a distorted square planar geometry. Characterization of both complexes with (1)H and (13)C NMR and UV-vis and electrospray ionization mass spectroscopies confirmed their integrity in DMSO solutions. Interaction of the complexes with human and bovine serum albumin has been studied with fluorescence spectroscopy, revealing their affinity for these proteins with relatively high values of binding constants. UV study of the interaction of the complexes with calf-thymus DNA (CT DNA) has shown that they can bind to CT DNA, and the corresponding DNA binding constants have been evaluated. Cyclic voltammograms of the complexes in the presence of CT DNA solution have shown that the interaction of the complexes with CT DNA is mainly through intercalation, which has been also shown by DNA solution viscosity measurements. Competitive studies with ethidium bromide (EB) have revealed the ability of the complexes to displace the DNA-bound EB, suggesting competition with EB. The combined work demonstrates the ability of pyridyl-dioxime chelates not only to lead to polynuclear 3d-metal complexes with impressive structural motifs and interesting magnetic properties but also to yield new, mononuclear 4d- and 5d-metal complexes with biological implications.

Metal-to-metal electron transfer in a cyanido-bridged {Fe2Co2} square complex followed by X-ray diffraction and absorption techniques.

The switching properties of a cyanido-bridged Fe/Co square molecule were investigated by single-crystal X-ray diffraction and X-ray absorption spectroscopy at both Fe and Co K-edges. Combining these two techniques, a complete picture of the thermal-, light- and X-ray-induced metal-to-metal electron transfer is obtained, illustrating the concerted role played by the Fe and Co sites.

Alpha-benzoin oxime in higher oxidation state 3d metal cluster chemistry: structural and magnetic study of a new Mn(III)(9) complex.

The initial employment of alpha-benzoin oxime (bzoxH(2)) in higher oxidation state 3d metal cluster chemistry has provided access to a new enneanuclear Mn(III) complex with an unprecedented metal-core topology consisting of two triangular [Mn(3)(mu(3)-Omicron(2-))(mu-OmicronNu)(3)](4+) fragments connected by a linear [Mn(3)(mu-OmicronNu)(6)](3+) unit. The Mn(III)(9) cluster is antiferromagnetically coupled and has an S = 3 spin ground state.

Towards models of the oxygen-evolving complex (OEC) of photosystem II: a Mn4Ca cluster of relevance to low oxidation states of the OEC.

Synthetic access has been achieved into high oxidation state Mn/Ca chemistry with the 4 : 1 Mn : Ca stoichiometry of the oxygen-evolving complex (OEC) of plants and cyanobacteria; the anion of (Et(3)NH)(2)[Mn(III)(4)Ca(O(2)CPh)(4)(shi)(4)] has a square pyramidal metal topology and an S = 0 ground state.