A Gadolinium(III) Complex Based on Pyridoxine Molecule with Single-Ion Magnet and Magnetic Resonance Imaging Properties.

Pyridoxine (pyr) is a versatile molecule that forms part of the family of B vitamins. It is used to treat and prevent vitamin B6 deficiency and certain types of metabolic disorders. Moreover, the pyridoxine molecule has been investigated as a suitable ligand toward metal ions. Nevertheless, the study of the magnetic properties of metal complexes containing lanthanide(III) ions and this biomolecule is unexplored. We have synthesized and characterized a novel pyridoxine-based GdIII complex of formula [GdIII(pyr)2(H2O)4]Cl3 · 2 H2O (1) [pyr = pyridoxine]. 1 crystallizes in the triclinic system and space group Pi. In its crystal packing, cationic [Gd(pyr)2(H2O)4]3+ entities are connected through H-bonding interactions involving non-coordinating water molecules and chloride anions. In addition, Hirshfeld surfaces of 1 were calculated to further investigate their intermolecular interactions in the crystal lattice. Our investigation of the magnetic properties of 1, through ac magnetic susceptibility measurements, reveals the occurrence of a slow relaxation in magnetization in this mononuclear GdIII complex, indicating an unusual single-ion magnet (SIM) behavior for this pseudo-isotropic metal ion at very low temperatures. We also studied the relaxometric properties of 1, as a potential contrast agent for high-field magnetic resonance imaging (MRI), from solutions of 1 prepared in physiological serum (0.0-3.2 mM range) and measured at 3 T on a clinical MRI scanner. The values of relaxivity obtained for 1 are larger than those of some commercial MRI contrast agents based on mononuclear GdIII systems.

Lipoic Acid-Functionalized Hexanuclear Manganese(III) Nanomagnets Suitable for Surface Grafting.

Highly anisotropic single-molecule magnets (SMMs) have attracted much interest in the field of molecular magnetism because of their spin features and potential technological applications. Additionally, a great effort has been devoted to the functionalization of such molecule-based systems which are made with ligands containing functional groups suitable to connect SMMs to junction devices or to perform their grafting on surfaces of different substrates. We have synthesized and characterized two lipoic acid-functionalized and oxime-based Mn(III) compounds, of formula [Mn6(µ3-O)2(H2N-sao)6(lip)2(MeOH)6][Mn6(µ3-O)2(H2N-sao)6(cnph)2(MeOH)6]}·10MeOH (1) and [Mn6(µ3-O)2(H2N-sao)6(lip)2(EtOH)6]·EtOH·2H2O (2) [H2N-saoH2 = salicylamidoxime, lip = lipoate anion, cnph = 2-cyanophenolate anion]. Compound 1 crystallizes in the space group Pi of the triclinic system and 2 crystallizes in the space group C2/c of the monoclinic system. In the crystal, neighboring Mn6 entities are linked using non-coordinating solvent molecules, which are H-bonded to N atoms of -NH2 groups of amidoxime ligand. In addition, Hirshfeld surfaces of 1 and 2 were calculated to study the variety of intermolecular interactions and the different levels of importance that take place in their crystal lattice; this type of computed study is the first time performed on Mn6 complexes. The study of the magnetic properties of 1 and 2 through dc magnetic susceptibility measurements reveals the coexistence of ferromagnetic and antiferromagnetic exchange couplings between the Mn(III) metal ions in both compounds, the latter being the predominant magnetic interaction. A spin S = 4 value of the ground state was obtained using isotropic simulations of the experimental magnetic susceptibility data for both 1 and 2. Ac magnetic susceptibility measurements show features typical of slow relaxation of the magnetization in 1 and 2, which indicate that SMM behavior takes place in both compounds.

Enantiomeric Complexes Based on Ruthenium(III) and 2,2'-Biimidazole: X-ray Structure and Magnetic Properties.

We have prepared and characterized two Ru(III) compounds based on the 2,2'-biimidazole (H2biim) ligand, namely, a single complex of formula cis-[RuCl2(H2biim)2]Cl·4H2O (1) and a racemic mixture of formula {cis-[RuCl2(H2biim)2]Cl}2·4H2O (2), which contains 50% of Ru(III) complex 1. Both compounds crystallize in the monoclinic system with space groups C2 and P21 for 1 and 2, respectively. These complexes exhibit the metal ion bonded to four nitrogen atoms from two H2biim molecules and two chloride ions, which balance part of the positive charges in a distorted octahedral geometry. Significant differences are observed in their crystal packing, which leads to the observation of differences in their respective magnetic behaviors. Despite having imidazole rings in both compounds, π-π stacking interactions occur only in the crystal structure of 2, and the shortest intermolecular Ru···Ru separation in 2 is consequently shorter than that in 1. Variable-temperature dc magnetic susceptibility measurements performed on polycrystalline samples of 1 and 2 reveal different magnetic behaviors at low temperatures: while 1 behaves pretty much as a magnetically isolated mononuclear Ru(III) complex with S = 1/2, 2 exhibits the behavior of an antiferromagnetically coupled system with S = 0 and a maximum in the magnetic susceptibility curve at approximately 3.0 K.

Holmium(III) Single-Ion Magnet for Cryomagnetic Refrigeration Based on an MRI Contrast Agent Derivative.

The coexistence of field-induced blockage of the magnetization and significant magnetocaloric effects in the low-temperature region occurs in a mononuclear holmium(III) diethylenetriamine-N,N,N',N″,N″-pentaacetate complex, whose gadolinium(III) analogue is a commercial MRI contrast agent. Both properties make it a suitable candidate for cryogenic magnetic refrigeration, thus enlarging the variety of applications of this simple class of multifunctional molecular nanomagnets.

Resolvin D1 and E1 promote resolution of inflammation in rat cardiac fibroblast in vitro.

Cardiac fibroblasts (CFs) have a key role in the inflammatory response after cardiac injury and are necessary for wound healing. Resolvins are potent agonists that control the duration and magnitude of inflammation. They decrease mediators of pro-inflammatory expression, reduce neutrophil migration to inflammation sites, promote the removal of microbes and apoptotic cells, and reduce exudate. However, whether resolvins can prevent pro-inflammatory-dependent effects in CFs is unknown. Thus, the present work was addressed to study whether resolvin D1 and E1 (RvD1 and RvE1) can prevent pro-inflammatory effects on CFs after lipopolysaccharide (LPS) challenge. For this, CFs were stimulated with LPS, in the presence or absence of RvD1 or RvE1, to analyze its effects on intercellular adhesion molecule 1 (ICAM-1), vascular cell adhesion protein 1 (VCAM-1), monocyte adhesion and the cytokine levels of tumor necrosis factor alpha (TNF-α), interleukin-6(IL-6), interleukin-1beta (IL-1ß), monocyte chemoattractant protein-1 (MCP-1) and interleukin-10 (IL-10). Our results showed that CFs are expressing ALX/FPR2 and ChemR23, RvD1 and RvE1 receptors, respectively. RvD1 and RvE1 prevent the increase of ICAM-1 and VCAM-1 protein levels and the adhesion of spleen mononuclear cells to CFs induced by LPS. Finally, RvD1, but not RvE1, prevents the LPS-induced increase of IL-6, MCP-1, TNF-α, and IL-10. In conclusion, our findings provide evidence that in CFs, RvD1 and RvE1 might actively participate in the prevention of inflammatory response triggered by LPS.

A Gadolinium(III) Complex Based on the Thymine Nucleobase with Properties Suitable for Magnetic Resonance Imaging.

The paramagnetic gadolinium(III) ion is used as contrast agent in magnetic resonance (MR) imaging to improve the lesion detection and characterization. It generates a signal by changing the relaxivity of protons from associated water molecules and creates a clearer physical distinction between the molecule and the surrounding tissues. New gadolinium-based contrast agents displaying larger relaxivity values and specifically targeted might provide higher resolution and better functional images. We have synthesized the gadolinium(III) complex of formula [Gd(thy)2(H2O)6](ClO4)3·2H2O (1) [thy = 5-methyl-1H-pyrimidine-2,4-dione or thymine], which is the first reported compound based on gadolinium and thymine nucleobase. 1 has been characterized through UV-vis, IR, SEM-EDAX, and single-crystal X-ray diffraction techniques, and its magnetic and relaxometric properties have been investigated by means of SQUID magnetometer and MR imaging phantom studies, respectively. On the basis of its high relaxivity values, this gadolinium(III) complex can be considered a suitable candidate for contrast-enhanced magnetic resonance imaging.

The effect of crystal packing and Re(IV) ions on the magnetisation relaxation of [Mn6]-based molecular magnets.

The energy barrier to magnetisation relaxation in single-molecule magnets (SMMs) proffers potential technological applications in high-density information storage and quantum computation. Leading candidates amongst complexes of 3d metals ions are the hexametallic family of complexes of formula [Mn6 O2 (R-sao)6 (X)2 (solvent)y ] (saoH2 =salicylaldoxime; X=mono-anion; y=4-6; R=H, Me, Et, and Ph). The recent synthesis of cationic [Mn6 ][ClO4 ]2 family members, in which the coordinating X ions were replaced with non-coordinating anions, opened the gateway to constructing families of novel [Mn6 ] salts in which the identity and nature of the charge balancing anions could be employed to alter the physical properties of the complex. Herein we demonstrate initial experiments to show that this is indeed possible. By replacing the diamagnetic ClO4 (-) anions with the highly anisotropic Re(IV) ion in the form of [Re(IV) Cl6 ](2-) , the energy barrier to magnetisation relaxation is increased by up to 30 %.

A Chiral, Photoluminescent, and Spin-Canted {Cu(I)Re(IV)2}n Branched Chain.

A new heteroleptic 1D Cu(I)-Re(IV) coordination polymer of the formula {Cu(I)Re(IV)Cl4(µ-Cl)(µ-pyz)[Re(IV)Cl4(µ-bpym)]}n·nMeNO2 (1; pyz = pyrazine, bpym = 2,2'-bipyrimidine) has been prepared through the Cu(I)-mediated self-assembly of two different Re(IV) metalloligands, namely, [ReCl5(pyz)](-) and [ReCl4(bpym)]. 1 consists of chiral branched chains with an overall rack-type architecture displaying photoemission and magnetic ordering. These results constitute a first step toward making new multifunctional magnetic materials based on mixed 3d-5d molecular systems.

Magnetocaloric efficiency tuning through solvent-triggered 3D to 2D interconversion in holmium(III)-based dynamic MOFs.

The neutral holmium(III) oxalate octadecahydrate {[Ho2(ox)3(H2O)6]·12H2O}n of mixed hexagonal/decagonal (63·103) 3D net topology shows important changes in the magnetocaloric efficiency upon dehydration/rehydration by heating and water vapor exposition to give the holmium(III) oxalate decahydrate {[Ho2(ox)3(H2O)6]·4H2O}n of hexagonal (63) 2D net topology through the intermediacy of the elusive amorphous anhydrous compound {Ho2(ox)3}n.

Highly anisotropic rhenium(IV) complexes: new examples of mononuclear single-molecule magnets.

The rhenium(IV) complex (NBu4)2[ReBr4(ox)] (1) (ox = oxalate and NBu4(+) = tetra-n-butylammonium cation) has been prepared and its crystal structure determined by X-ray diffraction. The structure is made up of discrete [ReBr4(ox)](2-) anions and bulky NBu4(+) cations. Each [ReBr4(ox)](2-) anion is surrounded by six NBu4(+) cations, which preclude any significant intermolecular contact between the anionic entities, the shortest rhenium···rhenium distance being 9.373(1) Å. Variable temperature dc and ac magnetic susceptibility measurements and field-dependent magnetization experiments on polycrystalline samples of 1 reveal the occurrence of highly anisotropic magnetically isolated Re(IV) centers (S(Re) = 3/2), which exhibit slow relaxation of the magnetization at very low temperatures in a dc field. Ac measurements conducted on a polycrystalline sample of the complex (NBu4)2[ReCl4(ox)] (2) [compound isostructural to 1 whose structure and dc magnetic susceptibility study were previously reported in Tomkiewicz, A.; Bartczak, T. J.; Kruszynski, R.; Mrozinski, J. J. Mol. Struct. 2001, 595, 225] show a similar behavior, both complexes thus constituting new examples of mononuclear single-molecule magnets. High-frequency and -field electron paramagnetic resonance on polycrystalline samples of 1 and 2 and on single crystals of 2 allowed for the determination for the first time of the negative sign and confirmed a significant magnitude and rhombicity (E/D) of the zero-field splitting tensor of the [ReCl4(ox)](2-) and [ReBr4(ox)](2-) centers, originating from a combination of spin-orbit coupling and low molecular symmetry. D and E values of 1 and 2 were estimated through magnetization measurements and theoretically calculated through complete active space and density functional theory methodologies.

Cubane-type Cu(II)4 and Mn(II)2Mn(III)2 complexes based on pyridoxine: a versatile ligand for metal assembling.

By using Vitamin B6 in its monodeprotonated pyridoxine form (PN-H) [PN = 3-hydroxy-4,5-bis(hydroxymethyl)-2-methylpyridine], two tetranuclear compounds of formula [Mn4(PN-H)4(CH3CO2)3Cl2]Cl·2CH3OH·2H2O (1) and [Cu4(PN-H)4Cl2(H2O)2]Cl2 (2) have been synthesized and magneto-structurally characterized. 1 crystallizes in the triclinic system with space group P1 whereas 2 crystallizes in the orthorhombic system with Fdd2 as space group. They exhibit Mn(II)2Mn(III)2 (1) and Cu(II)4 (2) cubane cores containing four monodeprotonated pyridoxine groups simultaneously acting as chelating and bridging ligands (1 and 2), three bridging acetate ligands in the syn-syn conformation (1), and two terminally bound chloride anions (1 and 2) plus two coordinated water molecules (2). The electroneutrality is achieved by the presence of chloride counterions in both compounds. Tri- [Mn(1) and Mn(3)] and divalent [Mn(2) and Mn(4)] manganese centers coexist in 1, all being six-coordinate with distorted Mn(1/3)O6 and Mn(2/4)O5Cl octahedral surroundings, respectively, the equatorial Mn-O bonds being about 0.2 Å shorter at the former ones. The two crystallographically independent copper(II) ions in 2 are five-coordinate in somewhat distorted CuO5 [Cu(1)] and CuO4Cl [Cu(2)] square pyramidal geometries. The values of the intracore metal-metal separation cover the ranges 3.144(1)-3.535(1) (1) and 2.922(6)-3.376(1) Å (2). The magnetic properties of 1 and 2 were investigated in the temperature range 1.9-300 K, and they correspond to an overall antiferromagnetic behavior with susceptibility maxima at 5.0 (1) and 65.0 K (2). The analysis of the magnetic susceptibility data showed the coexistence of intracore antiferro- and ferromagnetic interactions in the two compounds. Their values compare well with those existing in the literature for the parent systems.

The A-to-Z factors associated with cognitive impairment. Results of the DeCo study.

Introduction: Cognitive impairment (CI) is known to be mediated by several risk and protective factors, many of which are potentially modifiable. Therefore, it is important to have up-to-date studies that address a standard assessment of psychosocial, clinical and lifestyle variables. Materials and methods: We conducted a cross-sectional observational study, with a 24-month timeframe, to estimate the relationship between risk and protective factors associated with dementia, according to the A-to-Z Dementia Knowledge. Participants were considered at CI risk if they tested positive for at least one of three validated CI screening tests: The Memory Impairment Screening, Short Portable Mental State Questionnaire, and Semantic Verbal Fluency. The A-to-Z data Collection included Mediterranean Diet Adherence Screener and Geriatric Depression Scale. Results: The estimated prevalence of CI was 22.6% in a sample of 709 patients with an average of 69.3±10.3 years. The risk factors gradually associated with cognitive decline were hypertension, loneliness, and depression. In contrast, the protective factors gradually associated with less cognitive decline were internet use, reading, and intellectually stimulating jobs. Finally, living alone, having diabetes, taking benzodiazepines, and sleeping more than 9 h were statistically significant associated with CI, whereas to do memory training or a family history of dementia was characteristic of patients without CI. Conclusion: A joint assessment of the influence of psychosocial, clinical, and lifestyle-related factors is needed to develop dementia prevention strategies.

A new family of one-dimensional bromo-bridged Ir(IV)-Cu(II) complexes based on the hexabromoiridate(IV) metalloligand.

By using the iridium(IV) complex (NBu4)2[IrBr6] (1) as a metalloligand towards a Cu(II) metal ion, three novel Ir(IV) one-dimensional (1D) compounds of formula {IrBr5(µ-Br)Cu(Meim)4}n (2), {IrBr5(µ-Br)Cu(Viim)4}n (3) and {IrBr5(µ-Br)Cu(Buim)4}n (4), [Meim = 1-methylimidazole; Viim = 1-vinylimidazole; Buim = 1-butylimidazole] have been prepared and structurally and magnetically characterised. Compounds 2, 3 and 4 crystallise in the triclinic, monoclinic and orthorhombic crystal systems with space groups P1̄, C2/c and Pccn, respectively. Each Ir(IV) ion in 1-4 is six-coordinate and bonded to six bromide ions in a quasi regular octahedral geometry. In compounds 2-4, the CuII ion shows an axially elongated octahedron with four N atoms, from four monodentate imidazole derivative ligands, that form the equatorial plane and two bromide ions that occupy the axial positions. Cu(II) and Ir(IV) ions are linked through bridging bromide anions generating Ir(IV)-Cu(II) chains [with intrachain Cu(II)⋯Ir(IV) distances covering the range of ca. 5.10-5.42 Å]. In the crystal lattice of 2 and 3 are observed significant intermolecular Ir-Br⋯Br-Ir contacts and π⋯Br interactions, which organize arrangements that contribute to stabilizing the crystal structure of these Ir(IV)-based compounds. DC magnetic susceptibility measurements reveal that 1 displays magnetic behaviour typical of noninteracting mononuclear centres with S = 1/2. Besides, antiferromagnetic behaviour (2 and 3) and ferromagnetic (4) exchange coupling occur between the Cu(II) and Ir(IV) metal ions in the one-dimensional bromo-bridged compounds 2-4. Moreover, the study of the AC magnetic susceptibility shows a field-induced slow relaxation of the magnetisation for 1, indicating the presence of the single-ion magnet (SIM) phenomenon for the magnetically isolated hexabromoiridate(IV) complex.

Guest-induced magnetic exchange in paramagnetic [M2L4]4+ coordination cages.

Paramagnetic complexes that possess magnetically switchable properties show promise in a number of applications. A significantly underdeveloped approach is the use of metallocages, whose magnetic properties can be modulated through host-guest chemistry. Here we show such an example that utilises a simple [CuII2L4]4+ lantern complex. Magnetic susceptibility and magnetisation data shows an absence of exchange in the presence of the diamagnetic guest triflate. However, replacement of the bound triflate by ReBr62- switches on antiferomagnetic exchange between the Cu and Re ions, leading to an S = 1/2 ground state for the non-covalent complex [ReBr62-⊂CuII2L4]2+. Comparison of this complex to a "control" palladium-cage host-guest complex, [ReBr62-⊂PdII2L4]2+, shows that the encapsulated ReBr62- anions retain the same magnetic anisotropy as in the free salt. Theoretically calculated spin-Hamiltonian parameters are in close agreement with experiment. Spin density analysis shows the mode of interaction between the CuII and ReIV centres is through the Re-Br⋯Cu pathway, primarily mediated through the Cu(dx2-y2)|Brsp|Re(dyz) interaction. This is further supported by overlap integral calculations between singly occupied molecular orbitals (SOMOs) of the paramagnetic ions and natural bonding orbitals analysis where considerable donor-to-acceptor interactions are observed between hybrid 4s4p orbitals of the Br ions and the empty 4s and 4p orbitals of the Cu ions.

Angiotensin II Triggers NLRP3 Inflammasome Activation by a Ca2+ Signaling-Dependent Pathway in Rat Cardiac Fibroblast Ang-II by a Ca2+-Dependent Mechanism Triggers NLRP3 Inflammasome in CF.

Angiotensin II (Ang-II) is a widely studied hypertensive, profibrotic, and pro-inflammatory peptide. In the heart, cardiac fibroblasts (CF) express type 1 angiotensin II receptors (AT1R), Toll-like receptor-4 (TLR4), and the NLRP3 inflammasome complex, which play important roles in pro-inflammatory processes. When activated, the NLRP3 inflammasome triggers proteolytic cleavage of pro-IL-1, resulting in its activation. However, in CF the mechanism by which Ang-II assembles and activates the NLRP3 inflammasome remains not fully known. To elucidate this important point, we stimulated TLR4 receptors in CF and evaluated the signaling pathways by which Ang-II triggers the assembly and activity. In cultured rat CF, pro-IL-1ß levels, NLRP3, ASC, and caspase-1 expression levels were determined by Western blot. NLRP3 inflammasome complex assembly was analyzed by immunocytochemistry, whereas by ELISA, we analyzed NLRP3 inflammasome activity and [Formula: see text] release. In CF, Ang-II triggered NLRP3 inflammasome assembly and caspase-1 activity; and in LPS-pretreated CF, Ang-II also triggered [Formula: see text] secretion. These effects were blocked by losartan (AT1R antagonist), U73221 (PLC inhibitor), 2-APB (IP3R antagonist), and BAPTA-AM (Ca2+ chelator) indicating that the AT1R/PLC/IP3R/Ca2+ pathway is involved. Finally, bafilomycin A1 prevented Ang-II-induced [Formula: see text] secretion, indicating that a non-classical protein secretion mechanism is involved. These findings suggest that in CF, Ang-II by a Ca2+-dependent mechanism triggers NLRP3 inflammasome assembly and activation leading to [Formula: see text] secretion through a non-conventional protein secretion mechanism.

A novel adenine-based diruthenium(III) complex: Synthesis, crystal structure, electrochemical properties and evaluation of the anticancer activity.

Metal complexes based on purine nucleobases can be a very useful tool in the diagnosis and treatment of some diseases as well as in other biomedical applications. We have prepared and characterized a novel dinuclear ruthenium(III) complex based on the nucleobase adenine of formula [{Ru(µ-Cl)(µ-Hade)}2Cl4]Cl2·2H2O (1) [Hade = protonated adenine]. Complex 1 was characterized through Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy and energy dispersive X-ray analysis (SEM-EDX), magnetometer (SQUID) and cyclic voltammetry (CV) techniques. The crystal structure of 1 was determined by single-crystal X-ray diffraction. 1 crystallizes in the monoclinic system with space group P21/n. Each ruthenium(III) ion is six-coordinate and bonded to four Cl atoms [the average value of the RuIII-Cl bonds lengths is ca. 2.329(1) Å] and two N atoms (N3 and N9) from two adenine molecules, the N1 atom being protonated in both of them. The anticancer activity was evaluated through cell viability assays performed on a colon cancer (HCT116) and a gastric cancer cell lines (AGS), 1 showing an incipient anticancer effect on the AGS cell line at the highest concentration used in the study.

RUNAT-BI: A Ruthenium(III) Complex as a Selective Anti-Tumor Drug Candidate against Highly Aggressive Cancer Cell Lines.

Ruthenium compounds have demonstrated promising activity in different cancer types, overcoming several limitations of platinum-based drugs, yet their global structure-activity is still under debate. We analyzed the activity of Runat-BI, a racemic Ru(III) compound, and of one of its isomers in eight tumor cell lines of breast, colon and gastric cancer as well as in a non-tumoral control. Runat-BI was prepared with 2,2'-biimidazole and dissolved in polyethylene glycol. We performed assays of time- and dose-dependent viability, migration, proliferation, and expression of pro- and antiapoptotic genes. Moreover, we studied the growth rate and cell doubling time to correlate it with the apoptotic effect of Runat-BI. As a racemic mixture, Runat-BI caused a significant reduction in the viability and migration of three cancer cell lines from colon, gastric and breast cancer, all of which displayed fast proliferation rates. This compound also demonstrated selectivity between tumor and non-tumor lines and increased proapoptotic gene expression. However, the isolated isomer did not show any effect. Racemic Runat-BI is a potential drug candidate for treatment of highly aggressive tumors. Further studies should be addressed at evaluating the role of the other isomer, for a more precise understanding of its antitumoral potential and mechanism of action.

Enhancing the magnetic coupling of oxalato-bridged Re(IV)2M(II) (M=Mn, Co, Ni, and Cu) trinuclear complexes via peripheral halide ligand effects.

Four heterotrinuclear Re(IV)(2)M(II) compounds of general formula (NBu(4))(2)[{Re(IV)Br(4)(µ-ox)}(2)M(II)(Him)(2)] [NBu(4)(+) = tetra-n-butylammonium cation, ox = oxalate, Him = imidazole; M = Mn (1), Co (2), Ni (3), and Cu (4)] have been synthesized by using the novel mononuclear complex [Re(IV)Br(4)(ox)](2-) as a ligand toward divalent first-row transition metal ions in the presence of imidazole. Compounds 1-4 are isostructural complexes whose structure contains discrete trinuclear [{Re(IV)Br(4)(µ-ox)}(2)M(II)(Him)(2)](2-) anions and bulky NBu(4)(+) cations. The Re and M atoms are six-coordinated: four peripheral bromo and two oxalate-oxygens (at Re), and two cis-coordinated imidazole molecules and four oxygen atoms from two oxalate ligands (at M), build distorted octahedral surroundings. Two peripheral [ReBr(4)(ox)](2-) units act as bidentate ligands through the oxalate group toward the central [M(II)(Him)(2)] fragment affording the trinuclear entities. The values of the intramolecular Re···M separation are 5.62(1) (1), 5.51(1) (2), 5.46(1) (3), and 5.55(1) Å (4). Magnetic susceptibility measurements on polycrystalline samples of 1-4 in the temperature range of 1.9-300 K show the occurrence of intramolecular antiferro- [J = -1.1 cm(-1) (1)] and ferromagnetic interactions [J = +3.9 (2), +19.7 (3), and +14.4 cm(-1) (4)], the Hamiltonian being defined as H = -J [S(M)(S(Re1) + S(Re2))]. The larger spin delocalization on the oxalato bridge in 1-4 when compared to the trinuclear Re(IV)(2)M(II) complexes with chloro instead of bromo as peripheral ligands (1'-4') accounts for the strengthening of the magnetic interactions in 1-4 [J = -0.35 (1'), +14.2 (3'), and +7.7 cm(-1) (4')]. An incipient frequency dependence of the out-of-phase ac signals of 3 at very low temperatures is reminiscent of a system with slow relaxation of the magnetization, a phenomenon characteristic of single-molecule magnet behavior.

First magnetostructural study on a heterodinuclear 2,2'-bipyrimidine-bridged complex.

The use of the [ReCl(4)(bpym)] precursor as a ligand toward the fully solvated nickel(II) metal ion affords the first example of a 2,2'-bipyrimidine-bridged Re(IV)-Ni(II) complex, [ReCl(4)(µ-bpym)NiBr(2)(H(2)O)(2)] (1), whose intramolecular ferromagnetic coupling has been substantiated from both experimental and theoretical studies.

Detection of Hypoxanthine from Inosine and Unusual Hydrolysis of Immunosuppressive Drug Azathioprine through the Formation of a Diruthenium(III) System.

Hypoxanthine (hpx) is an important molecule for both biochemistry research and biomedical applications. It is involved in several biological processes associated to energy and purine metabolism and has been proposed as a biomarker for a variety of disease states. Consequently, the discovery and development of systems suitable for the detection of hypoxanthine is pretty appealing in this research field. Thus, we have obtained a stable diruthenium (III) compound in its dehydrated and hydrated forms with formula [{Ru(µ-Cl)(µ-hpx)}2Cl4] (1a) and [{Ru(µ-Cl)(µ-hpx)}2Cl4]·2H2O (1b), respectively. This purine-based diruthenium(III) system was prepared from two very different starting materials, namely, inosine and azathioprine, the latter being an immunosuppressive drug. Remarkably, it was observed that an unusual azathioprine hydrolysis occurs in the presence of ruthenium, thus generating hypoxanthine instead of the expected 6-mercaptopurine antimetabolite, so that the hpx molecule is linked to two ruthenium(III) ions. 1a and 1b were characterized through IR, SEM, powder and single-crystal X-ray Diffraction and Cyclic Voltammetry (CV). The electrochemical studies allowed us to detect the hpx molecule when coordinated to ruthenium in the reported compound. The grade of sensitivity, repeatability and stability reached by this diruthenium system make it potentially useful and could provide a first step to develop new sensor devices suitable to detect hypoxanthine.