Control of the geometry and anisotropy driven by the combination of steric and anion coordination effects in CoII complexes with N6-tripodal ligands: the impact of the size of the ligand on the magnetization relaxation time.

Four mononuclear CoII complexes of formula [Co(L)(SCN)2(CH3OH)0.5(H2O)0.5]·1.5H2O·0.75CH3OH (1), [Co(L1)Cl2]·H2O·2CH3CN (2), [Co(L1)(SCN)2]·1.5H2O·CH3OH (3) and [Co(L1)]ClO4·2CH3OH (4) were prepared from the N6-tripodal Schiff base ligands (S)P[N(Me)NC(H)2-Q]3 (L) and (S)P[N(Me)NC(H)1-ISOQ]3 (L1), where Q and ISOQ represent quinolyl and isoquinolyl moieties, respectively. In 1, the L ligand does not coordinate to the CoII ion in a tripodal manner but using a new N,N,S tridentate mode, which is due to the fact that the N6-tripodal coordination promotes a strong steric hindrance between the quinolyl moieties. However, L1 can coordinate to the CoII ions either in a tripodal manner using CoII salts with poorly coordinating anions to give 4 or in a bisbidentate fashion using CoII salt-containing medium to strongly coordinating anions to afford 2 and 3. In the case of L1, there is no steric hindrance between ISOQ moieties after coordination to the CoII ion. The CoII ion exhibits a distorted octahedral geometry for compounds 1-3, with the anions in cis positions for the former and in trans positions for the two latter compounds. Compound 4 shows an intermediate geometry between an octahedral and trigonal prism but closer to the latter one. DC magnetic properties, HFEPR and FIRMS measurements and ab initio calculations demonstrate that distorted octahedral complexes 1-3 exhibit easy-plane magnetic anisotropy (D > 0), whereas compound 4 shows large easy-axis magnetic anisotropy (D < 0). Comparative analysis of the magneto-structural data underlines the important role that is played not only by the coordination geometry but also the electronic effects in determining the anisotropy of the CoII ions. Compounds 2-3 show a field-induced slow relaxation of magnetization. Despite its large easy-axis magnetic anisotropy, compound 4 does not show significant slow relaxation (SMR) above 2 K under zero applied magnetic fields, but its magnetic dilution with ZnII triggers SMR at zero field. Finally, it is worth remarking that compounds 2-4 show smaller relaxation times than the analogous complexes with the tripodal ligand bearing in its arms pyridine instead of isoquinoline moieties, which is most likely due to the increase of the molecular size in the former one.

Synthesis, structures and magnetic studies of hexanuclear lanthanide complexes: SMM behavior of the DyIII analogue and MCE properties of the GdIII analogue.

The synthesis, structure and magnetic properties of homometallic hexanuclear lanthanide complexes [Ln6(HL)4(tfa)4(S)2]·2NO3·x H2O·yMeOH (1, Ln = Gd, S = MeOH, x = 0, y = 0; 2, Ln = Tb, S = H2O, x = 2, y = 2; 3, Ln = Dy, S = MeOH, x = 0, y = 2; 4, Ln = Er, S = MeOH, x = 0, y = 2). [(H4L) = 6-((bis(2-hydroxyethyl)amino)-N'-(2-hydroxybenzylidene)picolinohydrazide) (tfa = trifloroacetylacetone)] are reported. These hexanuclear assemblies are made up of two trinuclear triangular sub-units linked through the oxygen atoms of two phenoxide bridging groups in a corner sharing arrangement. Magnetic studies reveal that 1 displays a magnetocaloric effect with a maximum value of -ΔSm = 21.03 J kg-1 K-1 at T = 3 K and under an applied field change ΔB = 5 T. Complex 3 shows slow relaxation of magnetization even under zero applied field although a clear maximum in the ac susceptibility plots cannot be seen. However, under an optimal applied field of 0.2 T, clear maxima are observed in the out-of-phase (χ''M) component of the ac susceptibility in the temperature range 3.5 K (2 kHz) to 10.5 K (10 kHz). The temperature dependence of the relaxation times could be fitted to the sum of Orbach, Raman and QTM relaxation processes affording the following parameters: τo = 3.4(9) × 10-8 s, Ueff = 94(2) K, BRaman = 16.43(1) K-n s-1, n = 3.2(3) and τQTM = 0.0044(3) s. 4, under an applied magnetic field of 0.2 T, shows slow relaxation of magnetization through a thermally activated Orbach process with Ueff = 18.2(9) K and τo = 3.5(3) × 10-8 s.

Pushing up the easy-axis magnetic anisotropy and relaxation times in trigonal prismatic CoII mononuclear SMMs by molecular structure design.

The replacement of pyridine by 1-methyl-imidazol in the arms of a N6-tripodal ligand allows preparing two new CoII complexes with quasi-ideal triangular prismatic geometry, which behave as SIMs (Single Ion Magnets) at zero dc field with enhanced axial magnetic anisotropy, magnetic relaxation times and magnetic hysteresis.

Magneto-thermal properties and slow magnetic relaxation in Mn(II)Ln(III) complexes: influence of magnetic coupling on the magneto-caloric effect.

A family of Mn(II)Ln(III) dinuclear and tetranuclear complexes (Ln = Gd and Dy) has been prepared from the compartmental ligands N,N'-dimethyl-N,N'-bis(2-hydroxy-3-formyl-5-bromobenzyl)ethylenediamine (H2L1) and N,N',N''-trimethyl-N,N''-bis(2-hydroxy-3-methoxy-5-methylbenzyl)diethylenetriamine (H2L2). The Mn(II)Gd(III) complexes exhibit antiferromagnetic interactions between Mn(II) and Gd(III) ions in most cases, which are supported by Density Functional Theory (DFT) calculations. Experimental magneto-structural correlations carried out for the reported complexes and other related complexes found in bibliography show that the highest ferromagnetic coupling constants are observed in di-µ-phenoxido bridged complexes, which is due to the planarity of the Mn-(µ-O)2-Gd bridging fragment and to the high Mn-O-Gd angles. The effect of these angles has been studied by DFT calculations performed on a di-µ-phenoxido doubly bridged model. The magneto-thermal properties of the Mn(II)Gd(III) based complexes have also been measured, concluding that the magnitude of the Magneto-Caloric Effect (MCE) is due to the strength rather than to the nature of the magnetic coupling. Moreover, when two Mn(II)Gd(III) dinuclear units are connected by two carbonato-bridging ligands the MCE is enhanced, obtaining a maximum magnetic entropy change of 36.4 Jkg-1 K-1 at ΔB = 7 T and T = 2.2 K. On the other hand, one of the dinuclear Mn(II)Dy(III) complexes displays Single-Molecule Magnet (SMM) behaviour with an energy barrier of 14.8 K under an applied external field of 1000 Oe.

Dinuclear CoIIYIIIvs. tetranuclear CoY complexes: the effect of increasing molecular size on magnetic anisotropy and relaxation dynamics.

A new CoII2YIII2 complex with the formula [{Co(µ-L)Y(NO3)}2(µ-CO3)2]·2CH3OH·2H2O (where H2L = N,N',N''-trimethyl-N,N''-bis(2-hydroxy-3-methoxy-5-methylbenzyl)diethylenetriamine) has been prepared and its structure solved by single-crystal X-ray diffraction. The tetranuclear structure is formed by the connection of two [Co(µ-L)Y(NO3)] dinuclear units through two carbonate bridging ligands, which exhibit a µ3-κ2-O,O':κ-O:κ-O'' tetradentate coordination mode. The CoII ion exhibits a slightly distorted octahedral CoN3O3 coordination environment. From direct-current magnetic data a large and positive axial anisotropy parameter was extracted (D = +80.6 cm-1) and its sign unambiguously confirmed by HFEPR spectra and ab initio calculations. The extracted D value is rather larger than those previously reported for the analogous CoIIYIII dinuclear complexes, which agrees with the fact that the CoII ion in the CoII2YIII2 complex exhibits a lower distortion from the octahedral geometry in this family of CoIInYIIIn complexes. Dynamic ac magnetic measurements show that the reported compound presents field-induced slow relaxation for magnetization reversal, through a combination of direct and Raman processes. Magnetic measurements on the diluted magnetic counterpart (Zn/Co = 10/1) show the persistence of these processes, pointing out their single-ion origin. The Raman relaxation process for the CoII2YIII2 complex is faster that those observed for its CoIIYIII dinuclear counterparts. This fact and the existence of the persistent direct process at low temperature could be attributed to the former molecule being larger and more flexible than the latter ones.

Gold@Prussian blue analogue core-shell nanoheterostructures: their optical and magnetic properties.

Au@Prussian-Blue Analogue (PBA) shell nanoheterostructures are multifunctional nano-objects combining optical properties (surface plasmon resonance) of the Au core and magnetic properties of the PBA shell. We report in this article a series of new Au core@PBA shell nano-objects with different PBA shells: Au@K/Co/[FeII(CN)6] (2) and Au@K/Ni/[CrIII(CN)6]:[FeII(CN)6] (3) single PBA shell, as well as Au@K/Ni/[FeII(CN)6]@K/Ni/[FeIII(CN)6] (4) double PBA shell and Au@K/Ni/[FeII(CN)6]@K/Ni/[FeIII(CN)6]@K/Ni/[CrIII(CN)6] (5) triple PBA shell systems. The position and intensity of the Au SPR band, as well as the magnetic behaviour of the nanoheterostructures, are strongly affected by the shell composition and its thickness.

On the Magnetic Coupling and Spin Crossover Behavior in Complexes Containing the Head-to-Tail [FeII2(µ-SCN)2] Bridging Unit: A Magnetostructural Experimental and Theoretical Study.

A new dinuclear complex [{Fe(tpc-OBn)(NCS)(µ-NCS)}2] (1) based on the tripodal tpc-OBn ligand (tpc-OBn = tris(2-pyridyl)benzyloxymethane), containing bridging µ-κN:κS-SCN and terminal κN-SCN thiocyanate ligands, has been prepared and characterized by single crystal X-ray diffraction, magnetic studies, and DFT theoretical calculations. This complex represents the first example of dinuclear FeII complex with double µ-κN:κS-SCN bridges in a head-to-tail configuration that exhibits ferromagnetic coupling between metal ions (JFeFe = +1.08 cm-1). Experimental and theoretical magnetostructural studies on this kind of infrequent FeII dinuclear complex containing a centrosymmetrically [Fe2(µ-SCN)2] bridging fragment show that the magnitude and sign of the magnetic coupling parameter, JFeFe, depend to a large extent on the Fe-N-C (α) angle, so that JFeFe decreases linearly when α decreases. The calculated crossover point below which the magnetic interactions change from ferromagnetic to antiferromagnetic is found at 162.3°. In addition, experimental results obtained in this work and those reported in the literature suggest that large Ntripodal-FeII distances and bent N-bound terminal κN-SCN ligands favor the high spin state of the FeII ions, while short Ntripodal-FeII distances and almost linear Fe-N-C angles favor a stronger ligand field, which enables the FeII ions to show spin crossover (SCO) behavior.

Importance of Steric Influences in the Construction of Multicomponent Hybrid Polymetallic Clusters.

The straightforward room temperature synthesis of hybrid polymetallic manganese clusters is investigated, exploiting complementary ligand combinations of p-tert-butylcalix[4]arene and salicylaldoximes. Eight new [MnIII7MnII] clusters have been prepared wherein the simple substitution of alkyl or aryl groups at well-defined positions of the salicylaldoxime scaffold leads to two distinct structure types that, while exhibiting the same general topology, contain the unique MnII ion in different positions. Incorporation of a methyl, ethyl, or isopropyl group at the 3-position of the aromatic skeleton or a phenyl group at the oximic carbon gives structure type A that displays competing weak ferromagnetic and antiferromagnetic interactions. Substitution of a methyl or ethyl group at the oximic carbon atom invokes structure type B, incorporating an additional bulky chloride or nitrate into the metallic core due to the smaller steric imposition and position of the methyl or ethyl group. The distortion of the cluster core is consequently enhanced, switching the magnetic properties and resulting in single-molecule magnet behavior. The presence of tert-butyl groups at the 3- and 5-positions of the salicylaldoxime skeleton leads to a new [MnIV2MnIII2] cluster that is found to be a single-molecule magnet. The bulky tert-butyl group in the 3-position is too large to facilitate Mn8 cluster formation, and thus assembly occurs by an alternative pathway. Characteristic bonding modes of the constituent ligands are retained in every case, and the results presented here give insight into the potential of ligand combinations in future studies, highlighting the importance of steric factors in evaluating their relevant compatibilities.

Unprecedented tetranuclear complexes with "weighing balance shaped" topology: single crystal structures, unusual EPR spectra, magnetic properties and antioxidant activity.

Using the 2-hydroxy-N'-[(E)-phenyl(pyridin-2-yl)methylidene]benzohydrazide ligand and dicarboxylate anions (succinate and malonate), two new copper(ii) complexes of formula [Cu4(µ-L)4(µ-CH2(COO)2)(H2O)3](NO3)2·4H2O (1) and [Cu4(µ-L)4(µ-CH2-CH2(COO)2)(H2O)](NO3)2] (2) have been synthesized and characterized by single crystal X-ray diffraction. Complexes 1 and 2 contain a dicarboxylate bridged tetranuclear Cu(ii) cationic unit with "weighing balance shaped" topology. These compounds have also been studied by variable temperature magnetic susceptibility measurements, X-band EPR spectroscopy and electrochemistry. The unprecedented tetranuclear copper complexes 1 and 2 exhibit antiferromagnetic interactions between adjacent copper(ii) centers with magnetic exchange coupling constants (J) of J1 = -6.8 cm-1, J2 = -20.6 cm-1 and g = 2.03 for 1 and J1 = -3.1 cm-1, J2 = -13.9 cm-1 and g = 2.02 for 2. The goal for our research work is to understand the factors that govern the stability of the Cu-O(-O-C-O-) bond towards reactive oxygen species (ROS) in Cu-containing mimics utilizing a systematic approach. The antioxidant superoxide dismutase measurements indicate that these complexes behave as superoxide dismutase mimics.

Synthetic ability of dinuclear mesocates containing 1,3-bis(diazinecarboxamide)benzene bridging ligands to form complexes of increased nuclearity. Crystal structures, magnetic properties and theoretical studies.

Triple stranded Ni-metallacyclic complexes Na2.5[Ni2(bpcb)3]·0.5OH·18.5H2O (1) and Na2[Ni2(bpzcb)3]·16H2O (2), and double stranded Cu-metallacyclic complexes [Cu2(bpcb)2(H2O)2]·8H2O (3) and [Cu2(bpzcb)2(H2O)2]·4H2O (4) have been assembled from the tailored bisbidentate bridging ligands, 1,3-bis(pyrimidine-2-carboxamide)benzene (H2bpcb) and 1,3-bis(pyrazine-2-carboxamide)benzene (H2bpzcb), and the corresponding nitrate salts of the metal ions. Following the "complex as ligand" strategy, 1 can be assembled with either Ni2+, Co2+ ions or the [Mn(acen)Cl] complex to afford unique, neutral, bent trinuclear molecules [MIINi(bpcb)3]·xH2O (5 and 6) and the 2D honeycomb-like complex (PPh4){[Ni2(bpcb)3]2[Mn(acen)]3} (7), respectively. In these cases, the Ni2 units are linked to the corresponding metal ions through amidate oxygen atoms and the outward nitrogen atom of one of the pyrimidine rings of the bcpb ligand. The assembly of 2 with Ln3+ ions (Ln3+ = Tb, Gd) leads to one dimensional complexes of formula [{[Ni2(bpzcb)3]Tb(H2O)5}(CF3SO3)·THF·5H2O]n (8) and [{[Ni2(bpzcb)3]Ln(H2O)4(NO3)}·2THF·nH2O]n (9 and 10) (Ln3+ = Gd and Tb), where the dinuclear Ni2 units are joined to two Ln3+ ions exclusively through amidate oxygen atoms of two different ligands. The analyses of the magnetic data indicate that 1-4 exhibit intradinuclear ferromagnetic interactions between the metal ions through a spin polarisation mechanism, as supported by DFT calculations. Trinuclear complexes 5 and 6 show predominant antiferromagnetic coupling, which is a result of an antiferromagnetic interaction between one of the Ni2+ ions of the Ni2 unit and the M2+ ion through the pyrimidine bridging fragment that is stronger than the polarised ferromagnetic interaction between the Ni2+ ions through the bpcb ligand in the dinuclear [Ni2(bpcb)3]2- moiety. Complex 7 shows a dominant antiferromagnetic interaction between the Ni2+ and Mn2+, whereas the Ni2Ln (Ln3+ = Gd, Tb) chain complexes present ferromagnetic interactions inside the Ni2 mesocate unit as well as between the Ni2+ ions of the Ni2 unit and the Ln3+ ions. The magnetic exchange interactions in these new materials have been experimentally analysed and supported by theoretical DFT studies.

Analysis of Magnetic Anisotropy and the Role of Magnetic Dilution in Triggering Single-Molecule Magnet (SMM) Behavior in a Family of CoII YIII Dinuclear Complexes with Easy-Plane Anisotropy.

Three new closely related CoII YIII complexes of general formula [Co(µ-L)(µ-X)Y(NO3 )2 ] (X- =NO3- 1, benzoate 2, or 9-anthracenecarboxylato 3) have been prepared with the compartmental ligand N,N',N''-trimethyl-N,N''-bis(2-hydroxy-3-methoxy-5-methylbenzyl)diethylenetriamine (H2 L). In these complexes, CoII and YIII are triply bridged by two phenoxide groups belonging to the di-deprotonated ligand (L2- ) and one ancillary anion X- . The change of the ancillary bridging group connecting CoII and YIII ions induces small differences in the trigonally distorted CoN3 O3 coordination sphere with a concomitant tuning of the magnetic anisotropy and intermolecular interactions. Direct current magnetic, high-frequency and -field EPR (HFEPR), frequency domain Fourier transform THz electron paramagnetic resonance (FD-FT THz-EPR) measurements, and ab initio theoretical calculations demonstrate that CoII ions in compounds 1-3 have large and positive D values (≈50 cm-1 ), which decrease with increasing the distortion of the pseudo-octahedral CoII coordination sphere. Dynamic ac magnetic susceptibility measurements indicate that compound 1 exhibits field-induced single-molecule magnet (SMM) behavior, whereas compounds 2 and 3 only display this behavior when they are magnetically diluted with diamagnetic ZnII (Zn/Co=10:1). In view of this, it is always advisable to use magnetically diluted complexes, in which intermolecular interactions and quantum tunneling of magnetism (QTM) would be at least partly suppressed, so that "hidden single-ion magnet (SIM)" behavior could emerge. Field- and temperature-dependence of the relaxation times indicate the prevalence of the Raman process in all these complexes above approximately 3 K.

Engineered Au Core@Prussian Blue Analogous Shell Nanoheterostructures: Their Magnetic and Optical Properties.

We report a new approach for the synthesis of multifunctional Au core@Prussian Blue analogous (PBA) shell nanoheterostructures that involves PBA shell growth on the surface of cyanide-stabilized gold nanoparticles. It permits the assembly of Au@KNiII [FeII (CN)6 ] core@shell and Au@KNiII [FeII (CN)6 ]@KNiII [CrIII (CN)6 ] core@shell@shell heterostructures with well-defined and size-controlled gold cores and PBA shells. These heterostructures exhibit tunable size- and shape-dependent magnetic and optical properties: (i) the surface plasmon resonance band position and intensity mainly depend on the PBA shell thickness, and (ii) the magnetic properties (the transition temperature, the coercivity, and magnetic regime) depend in a complex manner on the thickness as well as the particular morphology of the magnetic shell.

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.

Facile interchange of 3d and 4f ions in single-molecule magnets: stepwise assembly of [Mn4 ], [Mn3Ln] and [Mn2Ln2 ] cages within calix[4]arene scaffolds.

The central Mn(II) ions in a series of calix[4]arene-stabilised butterflies can be sequentially replaced with Ln(III) ions, maintaining the structural integrity of the molecule but transforming its magnetic properties. The replacement of Mn(II) for Gd(III) allows for the examination of the transferability of spin-Hamiltonian parameters within the family as well as permitting their reliable determination. The introduction of the 4f ions results in weaker intramolecular magnetic exchange, an increase in the number of low-lying excited states, and an increase in magnetisation relaxation, highlighting the importance of exchange over single-ion anisotropy for the observation of SMM behaviour in this family of complexes. The presence of the [TM(II/III) (TBC[4])(OH)(solvent)] metalloligand (TM=transition metal, TBC=p-tBu-calix[4]arene) suggests that magnetic calix[n]arene building blocks can be employed to encapsulate a range of different "guests" within structurally robust "hosts".

Linked supramolecular building blocks for enhanced cluster formation.

Methylene-bridged calix[4]arenes have emerged as extremely versatile ligand supports in the formation of new polymetallic clusters possessing fascinating magnetic properties. Metal ion binding rules established for this building block allow one to partially rationalise the complex assembly process. The ability to covalently link calix[4]arenes at the methylene bridge provides significantly improved control over the introduction of different metal centres to resulting cluster motifs. Clusters assembled from bis-calix[4]arenes and transition metal ions or 3d-4f combinations display characteristic features of the analogous calix[4]arene supported clusters, thereby demonstrating an enhanced and rational approach towards the targeted synthesis of complex and challenging structures.

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.

Bifunctional Zn(II)Ln(III) dinuclear complexes combining field induced SMM behavior and luminescence: enhanced NIR lanthanide emission by 9-anthracene carboxylate bridging ligands.

There were new dinuclear Zn(II)-Ln(III) complexes of general formulas [Zn(µ-L)(µ-OAc)Ln(NO3)2] (Ln(III) = Tb (1), Dy (2), Er (3), and Yb (4)), [Zn(µ-L)(µ-NO3)Er(NO3)2] (5), [Zn(H2O)(µ-L)Nd(NO3)3]·2CH3OH (6), [Zn(µ-L)(µ-9-An)Ln(NO3)2]·2CH3CN (Ln(III) = Tb (7), Dy (8), Er (9), Yb(10)), [Zn(µ-L)(µ-9-An)Yb(9-An)(NO3)3]·3CH3CN (11), [Zn(µ-L)(µ-9-An)Nd(9-An)(NO3)3]·2CH3CN·3H2O (12), and [Zn(µ-L)(µ-9-An)Nd(CH3OH)2(NO3)]ClO4·2CH3OH (13) prepared from the reaction of the compartmental ligand N,N',N″-trimethyl-N,N″-bis(2-hydroxy-3-methoxy-5-methylbenzyl)diethylenetriamine (H2L), with ZnX2·nH2O (X = NO3(-) or OAc(-)) salts, Ln(NO3)3·nH2O, and, in some instances, 9-anthracenecarboxylate anion (9-An). In all these complexes, the Zn(II) ions invariably occupy the internal N3O2 site whereas the Ln(III) ions show preference for the O4 external site, giving rise to a Zn(µ-diphenoxo)Ln bridging fragment. Depending on the Zn(II) salt and solvent used in the reaction, a third bridge can connect the Zn(II) and Ln(III) metal ions, giving rise to triple-bridged diphenoxoacetate in complexes 1-4, diphenoxonitrate in complex 5, and diphenoxo(9-anthracenecarboxylate) in complexes 8-13. Dy(III) and Er(III) complexes 2, 8 and 3, 5, respectively, exhibit field induced single molecule magnet (SMM) behavior, with Ueff values ranging from 11.7 (3) to 41(2) K. Additionally, the solid-state photophysical properties of these complexes are presented showing that ligand L(2-) is able to sensitize Tb(III)- and Dy(III)-based luminescence in the visible region through an energy transfer process (antenna effect). The efficiency of this process is much lower when NIR emitters such as Er(III), Nd(III), and Yb(III) are considered. When the luminophore 9-anthracene carboxylate is incorporated into these complexes, the NIR luminescence is enhanced which proves the efficiency of this bridging ligand to act as antenna group. Complexes 2, 3, 5, and 8 can be considered as dual materials as they combine SMM behavior and luminescent properties.

Oxacalix[4]arene-supported di-, tetra- and undecanuclear copper(II) clusters.

Oxacalix[4]arenes containing either one or two oxa-bridges afford di and undecanuclear Cu(II) clusters respectively upon reaction with cupric nitrate under facile conditions. Variation in reaction conditions results in formation of a tetranuclear Cu(II) cluster with mono-oxacalix[4]arene, representing a structural expansion of the dinuclear assembly.

A bis-phenolate for the construction of linear lanthanide trimers.

The ligand bis(5-tert-butyl-2-hydroxy-3-hydroxymethyl-phenyl)methane, a flexible calix[n]arene analogue, is employed to construct an unusual linear [Ln3] trimer.

Diphenoxo-bridged Ni(II)Ln(III) dinuclear complexes as platforms for heterotrimetallic (Ln(III)Ni(II))2Ru(III) systems with a high-magnetic-moment ground state: synthesis, structure, and magnetic properties.

The first examples of pentanuclear heterotrimetallic [(LnNi)(2)Ru] [Ln(3+) = Gd (1) and Dy (2)] complexes were prepared and magnetostructurally characterized. They exhibit ferromagnetic interactions, leading to a high-magnetic-moment ground state.