Hetero-tri-spin systems: an alternative stairway to the single molecule magnet heaven?

The search for molecule-based magnetic materials has stimulated over the years the development of extremely rich coordination chemistry. Various combinations of spin carriers have been investigated and illustrated by a plethora of hetero-spin complexes: 3d-nd, 3d-4f, 2p-3d, and 2p-4f. More recently, two other classes of hetero-spin complexes have grown rapidly: compounds containing three different paramagnetic metal ions, or one radical and two different paramagnetic metal ions (all within the same molecular entity).

Luminescence thermometry based on one-dimensional benzoato-bridged coordination polymers containing lanthanide ions.

Three 1D coordination polymers with benzoate bridges have been assembled in the presence of 18-crown-6-ether (18C6): 1∞[Tb(PhCOO)3(H2O)(EtOH)]·0.5(18C6) 1, 1∞[Eu(PhCOO)3(H2O)2]·0.5(18C6) 2, 1∞[Nd(PhCOO)3(H2O)2]·0.

SMM Behavior Tuned by an Exchange Coupling LEGO Approach for Chimeric Compounds: First 2p-3d-4f Heterotrispin Complexes with Different Metal Ions Bridged by One Aminoxyl Group.

Coordination compounds containing three different spin carriers (2p, 3d, and 4f), with the general formula [MDy(LH)(hfac)] (M = Co, Ni, Mn, Zn), have been obtained using Mannich ligands decorated with a nitronyl-nitroxide fragment. The synthetic approach is general and leads to binuclear 3d-4f complexes, the two metal ions being bridged by one aminoxyl group and by one oxygen atom arising from a hfac ligand. Triangular spin topology affords significant 2p-3d, 3d-4f, and 2p-4f exchange interactions.

On the role played by the chirality of ligands on the aggregation of heterometallic Cu -Hg complexes.

Copper(II) complexes constructed from enantiopure Schiff-base ligands derived from o-vanillin and methionine or from their racemic mixture have been employed as metalloligands towards mercury(II) ions. The nature of the heterometallic Cu -Hg complexes (coordination polymers or oligonucler species), resulted from the reactions of the copper(II) complexes with HgCl or HgI , is different. The enantiopure metalloligands lead to chiral coordination polymers, [{Cu(R-/S-valmet)(H O)} HgCl ]·5H O·CH OH and [{Cu (R-/S-valmet) (μ-H O)(H O) }HgI ]·4H O.

Heterometallic 3d-4d coordination polymers assembled from trans-[Ru(L)(CN)] tectons and 3d cations.

Five new cyanido-bridged heterometallic coordination polymers have been obtained by reacting PPh4[RuIII(salpn)(CN)2]·H2O (1) and AsPh4[RuIII(valen)(CN)2]·8.5H2O (2) (H2salpn and H2valen being Schiff-base proligands resulting from the condensation reaction of salicylaldehyde with 1,3-propanediamine and, respectively, o-vanillin with 1,2-ethanediamine) with divalent transition metal perchlorate salts: ∞1[{RuIII(salpn)(CN)2}3{MII(DMF)3}2](ClO4)·4DMF (MII = Mn, 3; Co, 4) and ∞2[{RuIII(valen)(CN)2}4{MII(DMF)3}2{MII(DMF)4}](ClO4)2·4DMF (MII = Mn, 5; Co, 6; Ni, 7), respectively. The dicyanido species, trans-[Ru(salpn)(CN)2]- and trans-[Ru(valen)(CN)2]-, act as metalloligands with the 3d metal ions.

Aggregation of [Ln] clusters by the dianion of 3-formylsalicylic acid. Synthesis, crystal structures, magnetic and luminescence properties.

Three isostrucutral dodecanuclear clusters with the general formula [Ln12(fsa)12(μf3-OH)12(DMF)12]·nDMF (fsa2- is the dianion of 3-formylsalicylic acid; Ln = Eu 1, Gd 2, Dy 3) have been obtained from the reaction of fromylsalicyclic acid (H2fsa), tetrabutylammonium hydroxide and Ln(NO3)3·6H2O in methanol/DMF. Their structure consists of four vertex-sharing heterocubanes. Each heterocubane unit is assembled from four LnIII ions, three μ3-OH groups and one μ3-oxygen atom arising from the fsa2- carboxylato group.

Copper complexes for biomedical applications: Structural insights, antioxidant activity and neuron compatibility.

Copper coordinated with amino acid residues is essential for the function of many proteins. In addition, copper complexed to free l-Histidine, as [Cu(His)], is used in the treatment of the neurodegenerative Menkes disease and of cardioencephalomyopathy. This study was aimed to coordinate copper(II) with four small ligands (l-Serine, l-Histidine, Urea and Biuret) and to evaluate structural features, stability, antioxidant activity and neuronal compatibility of the resulting complexes.

Enantiopure versus Racemic Mixture in Reversible, Two-Step, Single-Crystal-to-Single-Crystal Transformations of Copper(II) Complexes.

The reaction of chiral sodium complexes, [Na(S-valmetH)]⋅H O (1-S) and [Na(R-valmetH)]⋅H O (1-R), with copper(II) acetate affords chiral one-dimensional coordination polymers with the formulas [Cu(S-valmet)(H O)]⋅H O (2-S) and [Cu(R-valmet)(H O)]⋅H O (2-R) (R/S-valmetH are Schiff base proligands resulting from the condensation reactions between o-vanillin and R/S-methionine). The copper ions are connected by the carboxylato groups belonging to the amino-acid moieties, resulting in infinite chains showing syn-anti out-of-plane bridging mode. The circular dichroism spectra of 1-S, 1-R, 2-S, and 2-R confirm their enantiomeric nature.

Heterotrimetallic complexes in molecular magnetism.

This paper reviews the most representative examples of heterometallic complexes containing three different paramagnetic metal ions, focusing on their magnetic properties. These compounds show a rich structural variety, ranging from discrete species to coordination polymers of various dimensionalities. The general synthetic strategies leading to heterotrimetallic complexes are discussed and illustrated.

Triphenylbismuth(v) di[(iso)nicotinates] - transmetallation agents or divergent organometalloligands? First organobismuth(v)-based silver(i) coordination polymers.

The reaction of PhBiCl with alkali salts of isonicotinic and nicotinic acids afforded PhBi[O(O)CCHN-4] (1) and PhBi[O(O)CCHN-3] (2), respectively, which were characterized by multinuclear NMR spectroscopy in solution, mass spectrometry and IR spectroscopy in the solid state. Their molecular structures were established by single-crystal X-ray diffraction. For both 1 and 2 the molecules contain a trigonal bipyramidal CBiO core, with the phenyl groups in equatorial positions.

Three different types of bridging ligands in a 3d-3d'-3d'' heterotrimetallic chain.

A one-pot synthesis of a 3d-3d'-3d'' heterotrimetallic coordination polymer with double diphenoxido, single cyanido and bis-bidentate oxalate as alternating bridges which exhibits an overall antiferromagnetic behaviour has been developed.

Synthesis, Crystal Structures, and EPR Studies of First MnLn Hetero-binuclear Complexes.

A new family of binuclear complexes [MnLn(dpm)(MeO)(MeOH)] is reported (where Ln = La (1), Pr (2), and Eu(3)). These compounds were obtained from a one-pot reaction between 2,2,6,6-tetramethyl-3,5-heptanodione (Hdpm), Mn, and the respective Ln salt in the presence of sodium methoxide. The derivative containing the diamagnetic ion La has been synthesized in order to characterize the local anisotropy of the Mn ion.

Cobalt(II) Ions Connecting [Co] Helicates into a 2-D Coordination Polymer Showing Slow Relaxation of the Magnetization.

The reactions of cobalt(II) perchlorate with a diazine tetratopic helicand, HL, in the presence of sodium carbonate afford two coordination polymers constructed from tetranuclear anionic helicates as building blocks: [CoLNa(HO)]·4HO (1) and [CoLNa(HO)]·2.7HO·DMF (2). The tetranuclear triple-stranded helicates, {CoL}, are connected in 1 by sodium(I) ions and in 2 by sodium(I) and cobalt(II) ions (HL results from the condensation reaction between 3-formylsalicylic acid and hydrazine).

A chimeric design of heterospin 2p-3d, 2p-4f, and 2p-3d-4f complexes using a novel family of paramagnetic dissymmetric compartmental ligands.

End-off bicompartmental ligands bearing a nitronyl-nitroxide arm have been designed for synthesizing various heterospin molecular systems. These ligands can selectively interact with 3d and 4f metal ions, leading to 2p-4f, 2p-3d, and 2p-3d-4f complexes. The magnetic properties of the 2p-4f and 2p-3d-4f complexes have been investigated and rationalized by theoretical calculations.

Synthesis, Crystal Structures, and Magnetic Properties of Two Novel Cyanido-Bridged Heterotrimetallic {CuMnCr} Complexes.

The self-assembly process between the heteroleptic [Cr(phen)(CN)] and [Cr(ampy)(CN)] metalloligands and the heterobimetallic {Cu(valpn)Mn} tecton afforded two heterotrimetallic complexes of formula [{Cu(valpn)Mn(μ-NC)Cr(phen)(CN)}{(μ-NC)Cr(phen)(CN)}]·2CHCN (1) and {[Cu(valpn)Mn(μ-NC)Cr(ampy)(CN)]·2CHCN} (2) [phen = 1,10-phenanthroline, ampy = 2-aminomethylpyridine, and Hvalpn = 1,3-propanedyilbis(2-iminomethylene-6-methoxyphenol)]. The crystal structure of 1 consists of neutral CuMnCr octanuclear units, where two [Cr(phen)(CN)] anions act as bis-monodentate ligands through cyanide groups toward two manganese(II) ions from two [Cu(valpn)Mn] units to form a [{Cu(valpn)Mn}Cr(CN)] square motif. Two [Cr(phen)(CN)] pendant anions in 1 are bound to the copper(II) ions with cis-trans geometry with respect to the bridging [Cr(phen)(CN)] anion.

Synthesis, Crystal Structures, Magnetic Properties, and Theoretical Investigation of a New Series of Ni-Ln-W Heterotrimetallics: Understanding the SMM Behavior of Mixed Polynuclear Complexes.

The polynuclear compounds containing anisotropic metal ions often exhibit efficient barriers for blocking of magnetization at fairly arbitrary geometries. However, at variance with mononuclear complexes, which usually become single-molecule magnets (SMM) under the sole requirement of a highly axial crystal field at the metal ion, the factors influencing the SMM behavior in polynuclear complexes, especially, with weakly axial magnetic ions, still remain largely unrevealed. As an attempt to clarify these conditions, we present here the synthesis, crystal structures, magnetic behavior, and ab initio calculations for a new series of Ni-Ln-W trimetallics, [(CN)W(CN)Ni(HO)(valpn)Ln(HO)]·HO (Ln = Y 1, Eu 2, Gd 3, Tb 4, Dy 5, Lu 6).

Binuclear Lanthanide-Radical Complexes Featuring Two Centers with Different Magnetic and Luminescence Properties.

Binuclear complexes with general formula [Ln(hfac)(HO)(dppnTEMPO)] (Ln = Gd, Tb, and Dy) have been obtained using the paramagnetic ligand 1-piperidinyl-4-[(diphenylphosphinyl)amino]-2,2,6,6-tetramethyl (dppnTEMPO) as a bridge. One of the lanthanide ions is ferromagnetically coupled with the TEMPO moiety. Two of the complexes (Dy and Tb) show slow relaxation of the magnetization, and the non-magneto-equivalence of the two Ln ions was clearly observed.

Slow Relaxation of Magnetization in an Isostructural Series of Zinc-Lanthanide Complexes: An Integrated EPR and AC Susceptibility Study.

We report the synthesis, structure, and spectroscopic and dynamic magnetic properties of a series of heterodinuclear complexes, [ZnLn(LH4 )2 ](NO3 )3 ⋅6 H2 O (Ln=Nd, Tb, Dy, Ho, Er, and Yb), with the singly deprotonated form of a new compartmentalized Schiff-base ligand, LH5 . The Ln(III) ions in these systems show a distorted square-antiprism geometry with an LnO8 coordination sphere. EPR spectroscopy and DC magnetic studies have shown that the anisotropic nature of the complexes is far more complicated than predicted on the basis of a simple electrostatic model.

A new family of [Cu(II)Ln(III)M(V)] heterotrimetallic complexes (Ln = La, Gd, Tb; M = Mo, W): model systems to probe exchange interactions and single-molecule magnet properties.

Four isostructural trinuclear 3d-4f-4(5)d heterotrimetallic complexes, with the general formula [L(2)CuLn(H2O)5(μ-NC)M(CN)7], were obtained from the association of binuclear 3d-4f complexes and {M(V)(CN)8}(3-) metalloligands (M = Mo, Ln = La ; M = W, Ln = La ; M = Mo, Ln = Gd ; M = Mo; Ln = Tb , where H2L(2) = 1,2-ethanediylbis(2-iminomethylene-6-methoxy-phenol)). The metalloligand coordinates through a single-cyanido group at the apical position of the copper(ii) ion belonging to the {Cu(II)Ln(III)} binuclear complex. The analysis of the magnetic data for the La(iii) derivatives (compounds and ), in the 1.

First coordination compounds based on a bis(imino nitroxide) biradical and 4f metal ions: synthesis, crystal structures and magnetic properties.

The synthesis, crystal structures and magnetic properties of two families of heterospin complexes containing lanthanide ions and a bis(imino nitroxide) biradical (IPhIN = 1-iodo-3,5-bis(4',4',5',5'-tetramethyl-4',5'-dihydro-1H-imidazole-1'-oxyl)benzene) are reported: in [Ln2(hfac)6(IPhIN)(H2O)2] compounds, two lanthanide ions [Ln = Gd(III) (1) and Dy(III) (2)] are coordinated to the biradical, and in [Ln(hfac)3(IPhIN)(H2O)] compounds, one lanthanide ion (Ln = Tb(III) (3), Gd(III) (4) or Dy(III) (5)) is coordinated to the biradical. Ferromagnetic intramolecular magnetic interactions between Gd(III) and the biradical were found for 1 and 4, while intramolecular magnetic interactions between the radicals were ferro- and antiferromagnetic, respectively. Compound 2 shows a field induced slow relaxation of magnetization, which (under an external applied field of 2 kOe) exhibits an activation energy barrier of ΔE/kB = 27 K and a pre-exponential factor of 1.

The exceptionally rich coordination chemistry generated by Schiff-base ligands derived from o-vanillin.

Ortho-vanillin became very popular in coordination chemistry because of its Schiff bases, which generate a rich variety of complexes, ranging from oligonuclear species to coordination polymers. Some of these organic molecules are particularly useful in metallosupramolecular chemistry for assembling homo- and heterometallic helicates. The Schiff bases obtained using aminoalcohols open the door to the synthesis of homo- and heterometallic clusters with various nuclearities and surprising topologies of the metal centers.

Magneto-structural variety of new 3d-4f-4(5)d heterotrimetallic complexes.

Three families of heterotrimetallic chains (type 1-type 3), with different topologies, have been obtained by reacting the 3d-4f complexes, [{Cu(L(1))}xLn(NO3)3] with x = 1 or 2, formed in situ by the reaction of Schiff-base bi-compartmental [Cu(II)(L(1))] complexes and lanthanide(iii) salts, with (NHBu3)3[M(CN)8] (M = Mo(V), W(V)). For type 1 series of compounds, 1-D coordination polymers, with the general formula [{Cu2(valpn)2Ln}{M(CN)8}]·nH2O·mCH3CN (where H2valpn = 1,3-propanediylbis(2-iminomethylene-6-methoxy-phenol), result from the association of trinuclear {CuLn(III)} moieties and [M(V)(CN)8](3-) anions acting as tri-connecting spacers [Ln = La (1), Ce (2), Eu (3), Tb (4), Ho (5), M = Mo; Ln = Tb (6), Ho (7), M = W; m = 0, n = 1.5 (7) and 2 (1-4, 6); n = 1, m = 1 (5)].

[Ru(III)(valen)(CN)2](-): a New Building Block To Design 4d-4f Heterometallic Complexes.

New 4d-4f heterometallic complexes with a one-dimensional structure, (1)∞[{Ru(valen)(CN)2KRu(valen)(CN)2}{Ln(O2NO)2(CH3OH)3}]·2CH3OH (Ln = Gd, Tb, Dy), have been assembled from the reaction of [K(H2O)2Ru(III)(valen)(CN)2]·H2O with lanthanide nitrates. The exchange interaction between Ru(III) and Gd(III) mediated by the cyanido ligand was determined for the first time and found to be weak and of antiferromagnetic nature.

Ascorbic acid decomposition into oxalate ions: a simple synthetic route towards oxalato-bridged heterometallic 3d-4f clusters.

Two types of oxalato-bridged heterometallic 3d-4f dodeca- and hexanuclear compounds have been obtained by connecting six bi- and, respectively, trinuclear moieties through oxalato bridges arising from the slow decomposition of the L-ascorbic acid.