Electroswitching of the single-molecule magnet behaviour in an octahedral spin crossover cobalt(ii) complex with a redox-active pyridinediimine ligand.

Thermal-assisted spin crossover and field-induced slow magnetic relaxation coexist in the solid state for the mononuclear cobalt(ii) complex with the non-innocent 2,6-bis(N-4-methoxyphenylformimidoyl)pyridine ligand. One-electron oxidation of the paramagnetic low-spin CoII ion (SCo = 1/2) to the diamagnetic low-spin CoIII ion (SCo = 0) leads to the electroswitching of the slow magnetic relaxation in acetonitrile solution.

Application of a Pillared-Layer Zn-Triazolate Metal-Organic Framework in the Dispersive Miniaturized Solid-Phase Extraction of Personal Care Products from Wastewater Samples.

The pillared-layer Zn-triazolate metal-organic framework (CIM-81) was synthesized, characterized, and used for the first time as a sorbent in a dispersive micro-solid phase extraction method. The method involves the determination of a variety of personal care products in wastewaters, including four preservatives, four UV-filters, and one disinfectant, in combination with ultra-high performance liquid chromatography and UV detection. The CIM-81 MOF, constructed with an interesting mixed-ligand synthetic strategy, demonstrated a better extraction performance than other widely used MOFs in D-µSPE such as UiO-66, HKUST-1, and MIL-53(Al). The optimization of the method included a screening design followed by a Doehlert design. Optimum conditions required 10 mg of CIM-81 MOF in 10 mL of the aqueous sample at a pH of 5, 1 min of agitation by vortex and 3 min of centrifugation in the extraction step; and 1.2 mL of methanol and 4 min of vortex in the desorption step, followed by filtration, evaporation and reconstitution with 100 µL of the initial chromatographic mobile phase. The entire D-µSPE-UHPLC-UV method presented limits of detection down to 0.5 ng·mL-1; intra-day and inter-day precision values for the lowest concentration level (15 ng·mL-1)-as a relative standard deviation (in %)-lower than 8.7 and 13%, respectively; average relative recovery values of 115%; and enrichment factors ranging from ~3.6 to ~34. The reuse of the CIM-81 material was assessed not only in terms of maintaining the analytical performance but also in terms of its crystalline stability.

Influence of Ligand Functionalization of UiO-66-Based Metal-Organic Frameworks When Used as Sorbents in Dispersive Solid-Phase Analytical Microextraction for Different Aqueous Organic Pollutants.

Four metal-organic frameworks (MOFs), specifically UiO-66, UiO-66-NH2, UiO-66-NO2, and MIL-53(Al), were synthesized, characterized, and used as sorbents in a dispersive micro-solid phase extraction (D-µSPE) method for the determination of nine pollutants of different nature, including drugs, phenols, polycyclic aromatic hydrocarbons, and personal care products in environmental waters. The D-µSPE method, using these MOFs as sorbents and in combination with high-performance liquid chromatography (HPLC) and diode-array detection (DAD), was optimized. The optimization study pointed out to UiO-66-NO2 as the best MOF to use in the multi-component determination. Furthermore, the utilization of isoreticular MOFs based on UiO-66 with the same topology but different functional groups, and MIL-53(Al) to compare with, allowed us for the first time to evaluate the influence of such functionalization of the ligand with regards to the efficiency of the D-µSPE-HPLC-DAD method. Optimum conditions included: 20 mg of UiO-66-NO2 MOF in 20 mL of the aqueous sample, 3 min of agitation by vortex and 5 min of centrifugation, followed by the use of only 500 µL of acetonitrile as desorption solvent (once the MOF containing analytes was separated), 5 min of vortex and 5 min of centrifugation. The validation of the D-µSPE-HPLC-DAD method showed limits of detection down to 1.5 ng·L-1, average relative recoveries of 107% for a spiked level of 1.50 µg·L-1, and inter-day precision values with relative standard deviations lower than 14%, for the group of pollutants considered.

Insights in the analytical performance of neat metal-organic frameworks in the determination of pollutants of different nature from waters using dispersive miniaturized solid-phase extraction and liquid chromatography.

Five metal-organic frameworks (MOFs), specifically HKUST-1, MOF-5(Zn), MIL-53(Al), UiO-64 and MOF-74(Zn) are synthesized, characterized, and utilized in a miniaturized solid-phase extraction method under dispersive mode (D-µSPE) for the determination of six pollutants of different nature, including one polycyclic aromatic hydrocarbon, two hormones, two drugs, and one disinfectant, from environmental waters (tap water and wastewater). A discussion of possible interactions justifying the partitioning of target analytes to the MOFs is included, considering not only the analytes' physicochemical characteristics but also those of MOFs: metal nature, structural environment of MOF pores, pore size and pore aperture widths, among others. MIL-53(Al) is selected for its versatility and high extraction efficiency for the target compounds. The D-µSPE method using MIL-53(Al) is optimized and used in combination with high-performance liquid chromatography (HPLC) with diode array detector (DAD) or liquid-chromatography with time-of-flight mass spectrometric detector (LC-TOF). Under optimum conditions, only 5mg of MIL-53(Al) are required for 10mL of water, with the aid of 5min of vortex and 5min of centrifugation. Elution is accomplished with 200µL of acetonitrile (3 times), and evaporation down to 100µL before LC injection. Detection limits down to 0.040µgL-1 for triclosan and 0.013µgL-1 for atrazine are obtained for the entire method using HPLC-DAD and LC-TOF, respectively. The method, operating at low spiked levels (2µgL-1 for HPLC-DAD and 0.7µgL-1 for LC-TOF), is also characterized for average relative recoveries of 109% and 105%; relative standard deviation values lower than 8.7% and 7.5%; and average extraction efficiencies of 41.2% and 49.1%; using HPLC-DAD and LC-TOF, respectively; while demonstrating adequate analytical performance with complex samples such as wastewaters.

A green metal-organic framework to monitor water contaminants.

The CIM-80 material (aluminum(iii)-mesaconate) has been synthetized in high yield through a novel green procedure involving water and urea as co-reactants. The CIM-80 material exhibits good thermal stability with a working range from RT to 350 °C with a small contraction upon desolvation. Moreover, this material is stable in water at different pH values (1-10) for at least one week, and shows a LC50 value higher than 2 mg mL-1. The new material has been tested in a microextraction methodology for the monitoring of up to 22 water pollutants while presenting little environmental impact: only 20 mg of CIM-80 and 500 µL of acetonitrile are needed per analysis. The analytical performance of the CIM-80 in the microextraction strategy is similar to or even better for several pollutants than that of MIL-53(Al). The average extraction efficiencies range from ∼20% for heavy polycyclic aromatic hydrocarbons to ∼70-100% for the lighter ones. In the case of the emerging contaminants, the average extraction efficiency can reach values up to 70% for triclosan and carbamazepine.

Photoluminescent and Slow Magnetic Relaxation Studies on Lanthanide(III)-2,5-pyrazinedicarboxylate Frameworks.

In the series described in this work, the hydrothermal synthesis led to oxidation of the 5-methyl-pyrazinecarboxylate anion to the 2,5-pyrazinedicarboxylate dianion (2,5-pzdc) allowing the preparation of three-dimensional (3D) lanthanide(III) organic frameworks of formula {[Ln2(2,5-pzdc)3(H2O)4]·6H2O}n [Ln = Ce (1), Pr (2), Nd (3), and Eu (4)] and {[Er2(2,5-pzdc)3(H2O)4]·5H2O}n (5). Single-crystal X-ray diffraction on 1-5 reveals that they crystallize in the triclinic system, P1̅ space group with the series 1-4 being isostructural. The crystal structure of the five compounds are 3D with the lanthanide(III) ions linked through 2,5-pzdc2- dianions acting as two- and fourfold connectors, building a binodal 4,4-connected (4·648)(426282)-mog network. The photophysical properties of the Nd(III) (3) and Eu(III) (4) complexes exhibit sensitized photoluminescence in the near-infrared and visible regions, respectively. The photoluminescence intensity and lifetime of 4 were very sensitive due to the luminescence quenching of the 5D0 level by O-H oscillators of four water molecules in the first coordination sphere leading to a quantum efficiency of 11%. Variable-temperature magnetic susceptibility measurements for 1-5 reveal behaviors as expected for the ground terms of the magnetically isolated rare-earth ions [2F5/2, 2H4, 4I9/2, 7F0, and 4I15/2 for Ce(III), Pr(III), Nd(III), Eu(III), and Er(III), respectively] with MJ = 0 (2 and 4) and ±1/2 (1, 3, and 5). Q-band electron paramagnetic resonance measurements at low temperature corroborate these facts. Frequency-dependent alternating-current magnetic susceptibility signals under external direct-current fields in the range of 100-2500 G were observed for the Kramers ions of 1, 3, and 5, indicating slow magnetic relaxation (single-ion magnet) behavior. In these compounds, τ-1 decreases with decreasing temperature at any magnetic field, but no Arrhenius law can simulate such a dependence in all the temperature range. This dependence can be reproduced by the contributions of direct and Raman processes, the Raman exponent (n) reaching the expected value (n = 9) for a Kramers system.

A magnetic-based dispersive micro-solid-phase extraction method using the metal-organic framework HKUST-1 and ultra-high-performance liquid chromatography with fluorescence detection for determining polycyclic aromatic hydrocarbons in waters and fruit tea infusions.

A hybrid material composed by the metal-organic framework (MOF) HKUST-1 and Fe3O4 magnetic nanoparticles (MNPs) has been synthetized in a quite simple manner, characterized, and used in a magnetic-assisted dispersive micro-solid-phase extraction (M-d-µSPE) method in combination with ultra-high-performance liquid chromatography (UHPLC) and fluorescence detection (FD). The application was devoted to the determination of 8 heavy polycyclic aromatic hydrocarbons (PAHs) in different aqueous samples, specifically tap water, wastewaters, and fruit tea infusion samples. The overall M-d-µSPE-UHPLC-FD method was optimized and validated. The method is characterized by: its simplicity in both the preparation of the hybrid material (simple mixing) and the magnetic-assisted approach (∼10min extraction time), the use of low sorbent amounts (20mg of HKUST-1 and 5mg of Fe3O4 MNPs), and the low organic solvent consumption in the overall M-d-µSPE-UHPLC-FD method (1.5mL of acetonitrile in the M-d-µSPE method and 2.8mL of acetonitrile in the UHPLC-FD run). The resulting method has high sensitivity, with LODs down to 0.8ngL(-1); adequate intermediate precision, with relative standard deviation values (RSD) always lower than 6.3% (being the range 5.9-9.0% in tap water for a spiked level of 45ngL(-1), 6.1-14% in wastewaters for a spiked level of 45ngL(-1), and 7.2-17% in fruit tea infusion samples for a spiked level of 45ngL(-1)); and adequate relative recoveries, with average values of 82% in tap water, and 94% and 75% in wastewater and fruit tea infusion samples, respectively, if using the proper matrix-matched calibration.

The metal-organic framework HKUST-1 as efficient sorbent in a vortex-assisted dispersive micro solid-phase extraction of parabens from environmental waters, cosmetic creams, and human urine.

Three metal-organic frameworks (MOFs), specifically HKUST-1, MOF-5, and MIL-53(Al), have been synthetized, characterized, studied and compared in a vortex-assisted dispersive micro-solid-phase extraction (VA-D-µ-SPE) procedure in combination with high-performance liquid chromatography (HPLC) with diode-array detection (DAD) for determining seven parabens in environmental waters (tap water, swimming pool water, and water coming from a spa pool), human urine (from two volunteers), and cosmetic creams (two commercial brands). Experimental parameters, such as nature and amount of MOF, sample volume, nature of elution solvent and its amount, vortex and centrifugation time, among others, were properly optimized. HKUST-1 was the most adequate MOF to work with. Detection limits for the overall method down to 0.1 µgL(-1) for butylparaben (BPB) and benzylparaben (BzPB) were obtained, with determination coefficients (R(2)) higher than 0.9966 for a range of 0.5-147 µgL(-1) (depending on the paraben), average relative recoveries (RR, in %) of 80.3% at the low spiked level (7 µgL(-1)), and relative standard deviation (RSD) values below 10% also at the low spiked level. The strength of the affinity between HKUST-1 and parabens was evaluated, and it ranged from 33.5% for isopropylparaben (iPPB) to 77.0% for isobutylparaben (iBPB). When analyzing complex environmental waters, RR values of 78%, inter-day precision values (as RSD) lower than 15%, and intra-day precision values lower than 7.8% were obtained, despite the observed matrix effect. When analyzing cosmetic creams, parabens were detected, with contents ranging from 0.14 ± 0.01 µgg(-1) for EPB in the healing cream analyzed to 1.12 ± 0.07 mgg(-1) for MPB in the mask cream analyzed, with precision values (RSD) lower than 12% and RR values from 63.7% for propylparaben (PPB) to 121% for iPPB. When analyzing human urine, no parabens were detected but the method could be performed with RSD values lower than 19%. These results show the adequateness of MOFs as sorbents in VA-D-µ-SPE procedures despite sample complexity.

Two-dimensional 3d-4f heterometallic coordination polymers: syntheses, crystal structures, and magnetic properties of six new Co(II)-Ln(III) compounds.

Six new heterometallic cobalt(II)-lanthanide(III) complexes of formulas [Ln(bta)(H2O)2]2[Co(H2O)6]·10H2O [Ln = Nd(III) (1) and Eu(III) (2)] and [Ln2Co(bta)2(H2O)8]n·6nH2O [Ln = Eu(III) (3), Sm(III) (4), Gd(III) (5), and Tb(III) (6)] (H4bta = 1,2,4,5-benzenetretracaboxylic acid) have been synthesized and characterized via single-crystal X-ray diffraction. 1 and 2 are isostructural compounds with a structure composed of anionic layers of [Ln(bta)(H2O)2]n(n-) sandwiching mononuclear [Co(H2O)6](2+) cations plus crystallization water molecules, which are interlinked by electrostatic forces and hydrogen bonds, leading to a supramolecular three-dimensional network. 3-6 are also isostructural compounds, and their structure consists of neutral layers of formula [Ln2Co(bta)2(H2O)8]n and crystallization water molecules, which are connected through hydrogen bonds to afford a supramolecular three-dimensional network. Heterometallic chains formed by the regular alternation of two nine-coordinate lanthanide(III) polyhedra [Ln(III)O9] and one compressed cobalt(II) octahedron [Co(II)O6] along the crystallographic c-axis are cross-linked by bta ligands within each layer of 3-6. Magnetic susceptibility measurements on polycrystalline samples for 3-6 have been carried out in the temperature range of 2.0-300 K. The magnetic behavior of these types of Ln(III)-Co(II) complexes, which have been modeled by using matrix dagonalization techniques, reveals the lack of magnetic coupling for 3 and 4, and the occurrence of weak antiferromagnetic interactions within the Gd(III)-Gd(III) (5) and Tb(III)-Tb(III) (6) dinuclear units through the exchange pathway provided by the double oxo(carboxylate) and double syn-syn carboxylate bridges.

Synthesis, crystal structure, and magnetic characterization of the three-dimensional compound [Co2(cbut)(H2O)3]n (H4cbut = 1,2,3,4-cyclobutanetetracarboxylic acid).

A novel cobalt(II) complex of formula [Co2(cbut)(H2O)3]n (1) (H4cbut = 1,2,3,4-cyclobutanetetracarboxylic acid) has been synthesized under hydrothermal conditions and its crystal structure has been determined by means of synchrotron radiation and neutron powder diffraction. The crystal structure of 1 consists of layers of cobalt(II) ions extending in the bc-plane which are pillared along the crystallographic a-axis through the skeleton of the cbut(4-) ligand. Three crystallographically independent cobalt(II) ions [Co(1), Co(2), and Co(3)] occur in 1. They are all six-coordinate with four carboxylate-oxygens [Co(1)-Co(3)] and two cis-[Co(1)] or trans-water molecules [Co(2) and Co(3)] building distorted octahedral surroundings. Regular alternating double oxo(carboxylate) [between Co(1) and Co(1a)] and oxo(carboxylate) plus one aqua and a syn-syn carboxylate bridges [between Co(1) and Co(2)] occur along the crystallographic b-axis, the values of the cobalt-cobalt separation being 3.1259(8) and 3.1555(6) Å, respectively. These chains are connected to the Co(3) atoms through the OCO carboxylate along the [011] direction leading to the organic-inorganic bc-layers with Co(1)-OCO(anti-syn)-Co(3) and Co(2)-OCO(anti-anti)-Co(3) distances of 5.750(2) and 4.872(1) Å. The shortest interlayer cobalt-cobalt separation through the cbut(4-) skeleton along the crystallographic a-axis is 7.028(2) Å. Variable-temperature magnetic susceptibility measurements show the occurrence of antiferromagnetic ordering with a Néel temperature of 5.0 K, followed by a field-induced ferromagnetic transition under applied dc fields larger than 1500 Oe. The magnetic structure of 1 has been elucidated at low temperatures in zero field by neutron powder diffraction measurements and was found to be formed by ferromagnetic chains running along the b-axis which are antiferromagnetically coupled with the Co(3) ions through the c-axis giving rise to noncompensated magnetic moments within each bc-layer (ferrimagnetic plane). The occurrence of an antitranslation operation between these layers produces a weak interlayer antiferromagnetic coupling along the a-axis which is overcome by dc fields greater than 1500 Oe resulting in a phase transition toward a ferromagnetic state (metamagnetic behavior).

Three new europium(III) methanetriacetate metal-organic frameworks: the influence of synthesis on the product topology.

Three new metal-organic framework structures containing Eu(III) and the little explored methanetriacetate (C7H7O6(3-), mta(3-)) ligand have been synthesized. Gel synthesis yields a two-dimensional framework with the formula [Eu(mta)(H2O)3]n·2nH2O, (I), while two polymorphs of the three-dimensional framework material [Eu(mta)(H2O)]n·nH2O, (II) and (III), are obtained through hydrothermal synthesis at either 423 or 443 K. Compounds (I) and (II) are isomorphous with previously reported Gd(III) compounds, but compound (III) constitutes a new phase. Compound (I) can be described in terms of dinuclear [Eu2(H2O)4](6+) units bonded through mta(3-) ligands to form a two-dimensional framework with topology corresponding to a (6,3)-connected binodal (4(3))(4(6)6(6)8(3))-kgd net, where the dinuclear [Eu2(H2O)4](6+) units are considered as a single node. Compounds (II) and (III) have distinct three-dimensional topologies, namely a (4(12)6(3))(4(9)6(6))-nia net for (II) and a (4(10)6(5))(4(11)6(4))-K2O2; 36641 net for (III). The crystal density of (III) is greater than that of (II), consistent with the increase of temperature, and thereby autogeneous pressure, in the hydrothermal synthesis.

Neutron diffraction studies of the molecular compound [Co2(bta)]n (H4bta =1,2,4,5-benzenetetracarboxylic acid): in the quest of canted ferromagnetism.

The exchange mechanism and magnetic structure of the organic-inorganic layered molecule-based magnet [Co2(bta)]n (1) (H4bta =1,2,4,5-benzenetetracarboxylic acid) have been investigated through variable-temperature magnetic susceptibility measurements and supported with a series of neutron diffraction experiments. Cryomagnetic studies have shown an antiferromagnetic ordering at a transition temperature of 16 K that is followed by the appearance of a weak ferromagnetism below 11 K. The weak antiferromagnetic interlayer interaction plays an important role in this system in spite of the long interlayer separation. A ferromagnetic ordering is induced by applied magnetic fields greater than 1800 G (metamagnetic behavior), and a slow magnetic relaxation from this ferromagnetic phase to the antiferromagnetic one is observed. The magnetic structure of 1 has been elucidated at low temperatures in zero field by neutron powder diffraction measurements and was found to be of antiferromagnetic nature with the local cobalt(II) spins (magnetic moments) being aligned ferromagnetically in the ac plane and antiferromagnetically coupled along the crystallographic b axis. No evidence for a long-range spontaneous ferromagnetic component below 11 K was observed in the neutron experiment.

Dicopper(II) Metallacyclophanes with Electroswitchable Polymethyl-Substituted para-Phenylene Spacers.

Double-stranded anionic dinuclear copper(II) metallacyclic complexes of the paracyclophane type [Cu2L2](4-) have been prepared by the Cu(II)-mediated self-assembly of different para-phenylenebis(oxamato) bridging ligands with either zero-, one-, or four-electron-donating methyl substituents (L=N,N'-para-phenylenebis(oxamate) (ppba; 1), 2-methyl- N,N'-para-phenylenebis(oxamate) (Meppba; 2), and 2,3,5,6-tetramethyl- N,N'-para-phenylenebis(oxamate) (Me4ppba; 3)). These complexes have been isolated as their tetra-n-butylammonium (1 a-3 a), lithium(I) (1 b-3 b), and tetraphenylphosphonium salts (1 c-3 c). The X-ray crystal structures of 1 a and 3 c show a parallel-displaced π-stacked conformation with a smaller deviation from perpendicularity between the two benzene rings and the basal planes of the square planar Cu(II) ions when increasing the number of methyl substituents (average dihedral angles (ϕ) of 58.72(7) and 73.67(5)° for 1 a and 3 c, respectively). Variable-temperature (2.0-300 K) magnetic-susceptibility measurements show an overall increase of the intramolecular antiferromagnetic coupling with the number of methyl substituents onto the para-phenylene spacers (-J=75-95, 100-124, and 128-144 cm(-1) for 1 a-c, 2 a-c, and 3 a-c, respectively; H=-JS1×S2). Cyclic voltammetry (CV) measurements show a reversible one-electron oxidation of the double polymethyl-substituted para-phenylenediamidate bridging skeleton at a relatively low formal potential that decreases with the number of methyl substituents (E1=+0.33, +0.24, and +0.15 V vs. SCE for 1-3, respectively). The monooxidized dicopper(II) π-radical cation species 3' prepared by the chemical oxidation of 3 with bromine exhibits intense metal-to-ligand charge-transfer (MLCT) transitions in the visible and near-IR (λmax=595 and 875 nm, respectively) regions together with a rhombic EPR signal with a seven-line splitting pattern due to hyperfine coupling with the nuclear spin of the two Cu(II) ions. Density functional (DF) calculations for 3' evidence a characteristic iminoquinonoid-type short-long-short alternating sequence of C-N and C-C bonds for both tetramethyl-para-phenylenediamidate bridges and a large amount of spin density of negative sign mainly delocalized along each of the four benzene C atoms directly attached to the amidate N atoms, which is in agreement with a fully delocalized π-stacked monoradical ligand description. Hence, the spins of the two Cu(II) ions (SCu=1/2) that are antiparallel aligned in 3 (OFF state) become parallel in 3' (ON state). Further developments may be then envisaged for this new permethylated dicopper(II) paracyclophane with a redox noninnocent ligand as a prototype for molecular magnetic electroswitch.

Copper(II) assembling with bis(2-pyridylcarbonyl)amidate and N,N'-2,2-phenylenebis(oxamate).

We herein present the synthesis and X-ray structures of five copper(II) complexes of formulae [Cu(bpca)(CF3SO3)(H2O)]·H2O (1), [Cu(bpca)(Phpr)(H2O)]·3/2H2O (2), {[Cu(bpca)]2[Cu(opba)(H2O)]}·H2O (3), {[Cu(bpca)]2(H2opba)}2·6H2O (4) and [Cu(bpca)(EtH2opba)]n (5), where bpca = bis(2-pyridylcarbonyl)amidate, Phpr = 3-phenylpropionate, CF3SO3(−) = triflate (anion of the trifluoromethanesulphonic acid), H4opba = N,N'-1,2-phenylenebis(oxamic acid), and EtH3opba = monoethyl ester derivative of the H4opba. 1 and 2 are mononuclear copper(II) complexes where the copper atom is five-coordinate in distorted square pyramidal surroundings with a tridentate bpca and a water molecule (1)/carboxylate oxygen (2) building the basal plane and a triflate oxygen (1)/water molecule (2) filling the apical position. 3 is a neutral tricopper(II) complex where the [Cu(opba)(H2O)]2− unit acts as a bis-bidentate ligand toward two peripheral [Cu(bpca)]+ fragments. The three crystallographically independent copper(II) ions in 3 are five-coordinate with two nitrogen and two oxygen atoms (inner copper atom)/three bpca-nitrogen and an oxamate oxygen (outer copper atom) building the basal plane plus a water molecule (inner copper)/an oxamate oxygen (outer copper) in the apical position (inner copper atom) of somewhat distorted square pyramidal surroundings. 4 is a centrosymmetric tetracopper(II) compound where four [Cu(bpca)]+ fragments are assembled by two H2opba2− groups adopting an unusual bidentate/bis-monodentate bridging mode. The two crystallographically independent copper(II) ions in 4 are also five-coordinate having the three bpca-nitrogens in basal positions, the other two sites of the distorted square pyramid being filled by two oxygens of either a bidentate oxamate (at one copper centre) or two bis-monodentate oxamates (at the other copper atom). 5 is a zigzag chain of [Cu(bpca)(H2O)]+ units which are connected through the EtH2opba− ligand adopting a bidentate/monodentate bridging mode across the monodeprotonated oxamate group. Each copper(II) ion in 5 is six-coordinate in an elongated octahedral CuN3O3 chromophore. The magnetic properties of 3­5 were investigated in the temperature range 1.9­300 K. 3 exhibits an intermediate intramolecular antiferromagnetic interaction [J = -65.8(2) cm(-1) with the Hamiltonian H = -J(S(Cu1)·S(Cu2) + S(Cu2)·S(Cu3))] which leads to a low-lying spin doublet at low temperatures. A weak antiferromagnetic coupling between the inner copper(II) ions occurs in 4 [J = -2.36(2) cm(-1), H = -JS1·S2)] and a very small intrachain antiferromagnetic interaction is observed in 5 [J = -0.17(1) cm(-1) with H = -J∑(i)S(i)·S(i+1)]. These values are analyzed by means of simple orbital symmetry considerations and compared with those previously reported for parent systems.

Low-dimensional 3d-4f complexes assembled by low-spin [Fe(III)(phen)(CN)4]- anions.

The synthesis, crystal structure, and magnetic properties of four new mixed 3d-4f complexes with formulas [{Fe(III)(phen)(CN)(4)}(4)Gd(2)(III)(bpym)(NO(3))(2)(H(2)O)(4)]·2CH(3)CN·2H(2)O}(n) (1), [{Fe(III)(phen)(CN)(4)}(4)Tb(2)(III)(bpym)(H(2)O)(8)]·(NO(3))(2)·2CH(3)CN}(n) (2), [{Fe(III)(phen)(CN)(4)}(4)Sm(III)(bpym)(NO(3))(2)(H(2)O)(5)]·2CH(3)CN}(n) (3), and [{Fe(III)(phen)(CN)(4)}(2)Pr(2)(III)(bpym)()(NO(3))(4)(H(2)O)(2)](n) (4) (phen = 1,10-phenanthroline and bpym = 2,2'-bipyrimidine) are discussed here. Compounds 1-3 are isomorphous and their structure consists of neutral ladder-like motifs where the rungs are made up by bpym-bridged dilanthanide(III) cations and the rods are defined by [Fe(phen)(CN)(4)](-) units adopting a bis-monodentate coordination mode through two of its four cyanide ligands. The electroneutrality in this family is achieved by either a chelating [at the Gd(III) (1) and Sm(III) (3)] or free [at the Tb(III) (2)] nitrate group and a peripheral [Fe(phen)(CN)(4)](-) entity, which act as a monodentate ligand across one of its four cyanide groups toward the rare-earth cation (1-3). Compound 4 exhibits a neutral two-dimensional structure where (µ-bpym)bis[diaquadi(nitrato-κ(2)-O,O')praseodymium(III)] fragments are interlinked through [Fe(phen)(CN)(4)](-) units adopting a tris-monodentate coordination mode across three of its four cyanide groups. Each iron(III) ion in 1-4 is six-coordinate with two nitrogen atoms from a chelating phen and four cyanide-carbon atoms building a somewhat distorted octahedral environment. The trivalent rare-earth cations are 9- (1-3) and 10-coordinate (4) having in common two nitrogen atoms from a bidentate bpym and three (1-3)/two (4) cyanide nitrogens, the coordination environment being completed by chelating nitrate (1, 3, 4) and water molecules (1-4). Magnetic susceptibility measurements in the 1.9-300 K temperature range show the occurrence of antiferromagnetic interactions in 1 through both the single cyanide- and the bis-bidentate bpym ligands. A weak ferromagnetic interaction is observed for 3 whereas very weak, if any, magnetic interactions would occur in 2 and 4, with the spin-orbit coupling of the low-spin iron(III) ion and the ligand field effects of the Tb(III) (2) and Pr(III) (4) masking their visualization.

[Fe(III)(dmbpy)(CN)4]-: a new building block for designing single-chain magnets.

We herein present the synthesis and magneto-structural study of a new family of heterobimetallic chains of general formula {[Fe(III)(dmbpy)(CN)(4)](2)M(II)(H(2)O)(2)}(n)·pnH(2)O [dmbpy = 4,4'-dimethyl-2,2'-bipyridine; M = Mn (2), Cu (3), Ni (4) and Co (5) with p = 4 (2), 3 (3), 9 (4) and 3.5 (5)] which were prepared by using the mononuclear PPh(4)[Fe(III)(dmbpy)(CN)(4)]·3H(2)O (1) building block (PPh(4)(+) = tetraphenylphosphonium) as a ligand toward fully solvated M(II) ions. The structure of 1 consists of discrete [Fe(III)(dmbpy)(CN)(4)](-) anions, tetraphenylphosphonium cations and noncoordinated water molecules. Complexes 2-5 are isostructural compounds whose structure consists of neutral 4,2-wave like heterobimetallic chains of formula {[Fe(III)(dmbpy)(CN)(4)](2)M(II)(H(2)O)(2)}(n) where the [Fe(III)(dmbpy)(CN)(4)](-) entity adopts a bis-monodentate coordination mode toward trans-[M(II)(H(2)O)(2)] units through two of its four cyanide groups in cis positions. 1 exhibits the magnetic behaviour of magnetically isolated six-coordinate low-spin Fe(III) complexes with an important orbital contribution. 2 behaves as ferrimagnetic Fe(III)(2)Mn(II) chains, whereas 3-5 exhibit intrachain ferromagnetic couplings between the low-spin Fe(III) and either Cu(II) (3), Ni (4) or Co(II) (5) as well as frequency-dependence of the out-of-phase ac susceptibility signals below 3.0 (3), 5.5 (4) and 5.0 K (5). The relaxation time and the energy to reverse the magnetization of 3-5 are related to the anisotropy of the M(II) center and to the intra- and interchain magnetic interactions. Unprecedentedly in the world of cyanide-bearing complexes, 5 exhibits a double slow relaxation of the magnetization.

Selective gas and vapor sorption and magnetic sensing by an isoreticular mixed-metal-organic framework.

A novel isoreticular oxamato-based manganese(II)-copper(II) open metal-organic framework H(2)O@iso1 featuring a pillared square/octagonal layer structure with alternating open and closed octagonal pores has been rationally prepared. The open-framework topology is responsible for a large selectivity in the separation of small gas (CO(2) over CH(4)) and vapor molecules (CH(3)OH over CH(3)CN and CH(3)CH(2)OH). H(2)O@iso1 displays a long-range three-dimensional ferromagnetic ordering with a drastic variation of the critical temperature as a function of the guest molecule [T(C) < 2.0 K (CO(2)@iso1 and CH(4)@iso1) and T(C) = 6.5 (CH(3)OH@iso1) and 21.0 K (H(2)O@iso1)].

Molecular engineering to control the magnetic interaction between single-chain magnets assembled in a two-dimensional network.

Two two-dimensional (2D) systems having the formula [{Fe(III)(dmbpy)(CN)(4)}(2)Co(II)L](n) [L = pyetNO (1), tvpNO (2)] and consisting of single-chain magnets connected through organic ligands (L) have been prepared, and their magnetic properties have been investigated. The overall magnetic behavior depends on the capacity of the organic pillars to transmit long-range magnetic interactions. 1 is the first example of a 2D compound exhibiting double relaxation of the magnetization, whereas 2 behaves as a metamagnet.

Redox switching of the antiferromagnetic coupling in permethylated dicopper(II) paracyclophanes.

A unique magnetic electroswitching behavior has been observed in an oxamato-based permethylated dicopper(II) paracyclophane; upon reversible one-electron oxidation of the double tetramethyl-substituted p-phenylenediamidate bridging skeleton, the spin alignment of the two Cu(II) ions (S(Cu) = ½) changes from antiparallel (OFF) to parallel (ON) in the resulting dicopper(II) π-radical cation species.