Search

Two isostructural lanthanide(iii)-based coordination polymers with square antiprismatic environment are described. Magnetic properties are studied from experimental and theoretical viewpoints to analyze their SIM behavior.

Herein, we report on the synthesis, structural analysis, physicochemical characterization and photoluminescence performance of two ternary compounds based on dicarboxylate and bispyridyl-like ligands and metal ions of group 12, namely [Zn2(μ4-bdc)(μ-pbptz)(DMF)2(NO3)2]n (1-Zn) and {[Cd(μ3-bdc)(μ-pbptz)]·DMF}n (2-Cd) (where bdc = benzene-1,4-dicarboxylate, pbptz = 3,6-bis(4-pyridyl)-1,2,4,5-tetrazine, and DMF = N,N-dimethylformamide). 1-Zn, consisting of a 2D-layered framework, can be considered as the lower-dimensional analogue of the previously reported {[Zn2(μ4-bdc)2(μ-pbptz)]·2DMF·3H2O}n 3D MOF (1′-Zn), which is shown to recrystallize into 1-Zn undergoing a kind of exfoliation. 2-Cd presents a 3D doubly interpenetrated framework whose porosity is reduced to approximately half of the available solvent-accessible voids contained in the non-interpenetrated homologue reported so far, {[Cd(μ3-bdc)(μ-pbptz)]·3DMF}n (2′-Cd). Structural factors leading to each of the alternative frameworks are detailed by analysing the building units with a perusal of the Cambridge Structural Database and providing a comparative description of the structures. The photoluminescence properties of herein reported compounds (1-Zn and 2-Cd) are also measured and the processes governing the spectra are described using time-dependent density-functional theory (TD-DFT), which allows establishing some structural correspondences by comparing these results with those of the 1′-Zn and 2′-Cd analogues.

Eleven new dinuclear and tetranuclear compounds of general formulae [Zn(μ-L)(μ-X)Ln(NO3)2]·nS, [Zn2Dy2(μ3-L')2(μ-sal)2(NO3)(CH3OH)](NO3)·5CH3OH and [Zn2Er2(μ3-L')2(μ-sal)2(CH3OH)2](NO3)2·4CH3OH (X = benzoate, anthracenate, diclofenac, salicylate, 2,6-dihydroxybenzoate; Ln = Dy, Er; S = water, acetonitrile, methanol) were prepared from the N,N'-dimethyl-N,N'-bis(2-hydroxy-3-formyl-5-bromobenzyl)ethylenediamine compartmental ligand (H2L). Complexes 1-6 and 9-11 consist of diphenoxido-carboxylate triply bridged compounds, which differ mainly in the carboxylate bridging ligand. It should be noted that the acidic character of the salicylic acid promotes, in the presence of methanol, the methoxylation of the H2L ligand thereby yielding a hemiacetal H3L', which is able to connect the Ln(iii) ions of two ZnLn dinuclear units forming the Zn2Ln2 tetranuclear complexes 7 and 8. All compounds display SMM behaviour in the presence of an external field with effective energy barriers (Ueff) as high as 61 K. Magneto-structural data for these complexes reveal that their SMM behaviour is not only significantly affected by the type of Ln(iii) ion but also by the carboxylate bridging ligand connecting the Zn(ii) and Ln(iii) ions. Photoluminescence properties have also been accomplished, showing that the ligands are able to sensitize lanthanide centred emissions in the visible and near-infrared regions with variable capacity. Moreover, the analysis of the luminescence decay curves reveals emission lifetimes in the range of few microsecond or hundreds of nanoseconds for Dy(iii)-based or Er(iii)-based luminophores, respectively.

We have designed and synthesized eight isostructural 1D coordination polymers (CPs) with the general formula {[Ln(aapc)3(DMF)]}n [where Ln(iii) = Y (2), La (3), Nd (4), Eu (5), Gd (6), Tb (7), Dy (8), Er (9); and aapc = 3-((anthraquinone-1-yl)amino)propanoate]. These CPs consist of Ln-carboxylate infinite rods in which the bulky anthraquinone scaffolds arise from it in such a way that the resulting supramolecular packing exhibits isolated 1D chains. Solution structures have been corroborated through NMR methods including PGSE and EXSY NMR studies and, due to the presence of lanthanide ions, magnetic and luminescence properties have been studied. Alternating current magnetic measurements of compound 8 show slow relaxation of the magnetization, a characteristic of single molecule magnets (SMMs). The evaluation of solid-state photophysical properties reveals that the aapc scaffold sensitizes lanthanide(iii) based emission of compounds 4-9 both in the visible and near-infrared (NIR) regions at 10 K.

Herein, we report the detailed structural characterization and photoluminescence (PL) properties of two new isostructural coordination polymers (CPs) based on 2-aminonicotinate (2ani) ligand and zinc(ii) or cadmium(ii) metal ions, namely, [M(μ-2ani)2]n [MII = Zn(1) and Cd(2)]. These compounds are characterized as chiral 2D-layered structures, resulting from the bridging of the 2ani ligands in the MN2O4 coordination shell. Also, strong supramolecular interactions are found to sustain the overall crystal structure, which endows these materials with high stability. The single crystals of 1 exhibit waveguiding behaviour along some preferred orientations. The examination of the polycrystalline samples of both compounds under UV light also shows that the samples exhibit remarkably strong PL emissions, which consist of blue fluorescence and green phosphorescence involving long-lasting phosphorescence (LLP) at low temperature. Fitting of the decay curves confirms the occurrence of short (in the order of nanoseconds) and very large lifetimes (τ ≈ 320 and 560 ms for 1 and 2, respectively) of the wavelengths responsible for their blue and green emissions, respectively, which have been studied using DFT calculations.

The preparation and characterization of various alkyl, allyl or alkene Rh(iii) and Ir(iii) complexes as well as studies on the intramolecular reactions leading to transformation of one into another are reported. The silyl-hydrido-Rh(iii) complex {Rh(H)[SiMe(o-C6H4SMe)2](PPh3)}[BArF4], with a vacant coordination site, reacts with 1,5-cyclooctadiene (cod) leading to olefin insertion into the Rh-H bond and rearrangement to yield the 16e cyclooctenyl-Rh(iii) complex {Rh(η3-cyclooctenyl)[SiMe(o-C6H4SMe)2]}[BArF4] (1). This compound can be also synthesized by reaction of the 18e chloride precursor {Rh(η3-cyclooctenyl)[SiMe(o-C6H4SMe)2]Cl} with NaBArF4. The reaction of the thioether-silane SiMeH(o-C6H4SMe)2 with [Rh(nbd)Cl]2 (nbd = norbornadiene) leads to {Rh(σ-ntyl)[SiMe(o-C6H4SMe)2]Cl} (ntyl = nortricyclyl) (2). The abstraction of chloride from this neutral 16e ntyl-Rh(iii) complex with NaBArF4 results in the unusual isomerization of σ-nortricyclyl into σ,π-norbornenyl forming the 16e and cationic {Rh(σ,π-nbyl)[SiMe(o-C6H4SMe)2][BArF4] (nbyl = norbornenyl)} compound 3. Coordinatively saturated {Ir(η3-cyclooctenyl)[SiMe(o-C6H4SMe)2]Cl} (4) has been synthesized by the reaction of [Ir(cod)Cl]2 with SiMeH(o-C6H4SMe)2. The reaction of 4 with NaBArF4 led to the formation of the unsaturated and cationic Ir(iii) compound {Ir(η3-cyclooctenyl)[SiMe(o-C6H4SMe)2]}[BArF4] (5). Compound 5 shows low stability in solution and undergoes successive β-hydride elimination and olefin insertion steps, which were elucidated by DFT calculations, to form 18e {Ir(H)[SiMe(o-C6H4SMe)2](η4-cod)}[BArF4] (6).

Expanding the possibilities of the use of simple and available ZnEt

We report here 1,1- and 1,2-insertion reactions of small unsaturated molecules in the N–B bonds of two boron guanidinates, (Me2N)C(NiPr)2BCy2 (1) and {iPr(H)N}C(NiPr){N(p-tBu-C6H4)}BCy2 (2), and two bisboron guanidinates(2–), {iPr(BCy2)N}C(NiPr){N(p-tBu-C6H4)}BCy2 (3) and {iPr(C8H14B)N}C(NiPr){N(p-Me-C6H4)}BC8H14 (4), the latter being prepared for the first time by double deprotonation of the corresponding guanidine with the 9-borabicyclo[3.3.1]nonane dimer, (H-BC8H14)2. Compounds 1–4 easily insert aromatic isonitriles, XylNC (Xyl = 2,6-Me2-C6H3) and (p-MeO-C6H4)NC, to give the expected diazaboroles 5–12, some of them being structurally characterised by X-ray diffraction. Interestingly, the BC8H14 derivatives 11 and 12 are in a fast temperature-dependent equilibrium with the de-insertion products, whose thermodynamic parameters are reported here. A correlation between these equilibria and the puckered heterocyclic structure found in the solid state for 11, and confirmed by DFT calculations, is also established. Reactions of the aforementioned guanidinates with CO are more sluggish or even precluded, and only one product, {iPr(H)N}C{N(p-tBu-C6H4)}(NiPr)(CO)BCy2 (13), could be isolated in moderate yields. The 1,2-insertions of benzaldehyde in compounds 1, 2 and 4 are reversible reactions in all cases, and only one of the insertion products, {iPr(H)N}C{N(p-tBu-C6H4)}(NiPr)(PhHCO)BCy2 (16a), was isolated and diffractrometrically characterised. Likewise, CO2 reversibly inserts into a N–B bond of 2 to give {iPr(H)N}C{N(p-tBu-C6H4)}(NiPr)(CO2)BCy2 (19) with a conversion of ca. 9%. In all these equilibria, de-insertion is always favoured upon increasing the temperature.

A series of trimetallic Zn-Dy-Zn complexes of the general formula [ZnX(μ-L)Dy(μ-L)XZn]Y·nS, where H

A new iron(III) complex [Fe(H2Vi)3]·py·4H2O (1) {H3Vi = violuric acid, py = pyridine} was self-assembled and characterized. In the crystal structure, adjacent [Fe(H2Vi)3] blocks are H-bonded into a complex 3D network, which was topologically classified as a pcu [alpha-Po primitive cubic] network. Importance of π-stacking interactions was also highlighted and analyzed computationally. Magnetic studies confirmed antiferromagnetic exchange coupling, while ZFCM/FCM experiments indicated an ordering temperature Tc = 50 K. Finally, magnetic hysteresis at 5 K possesses the coercive field of Bc = 69 mT.

The synthesis of novel dialkylboron guanidinates is reported: the symmetrical compounds, (Me2N)C(NR)2BR′2 [R = iPr, R′ = Nrb (1); R = Cy, R′ = Nrb (2); R = iPr, R′ = Cy (3); R = R′ = Cy (4); R = 2,6-iPr2-C6H3; R′ = Cy (5); Nrb = exo-2-norbornyl] and the asymmetrically coordinated {iPr(H)N}C(NiPr)(NAr)BCy2 [Ar = Ph (6), 4-Me-C6H4 (7), 4-tBu-C6H4 (8)] were prepared by the salt metathesis method from the appropriate lithium guanidinates and chloroboranes. Moreover, the bis(dicyclohexylboron)guanidinate(−2) {iPr(Cy2B)N}C(NiPr){N(4-tBu-C6H4)}BCy2 (9) was also prepared from the corresponding dilithium guanidinate Li2[{N(4-tBu-C6H4)}C(NiPr)2] and ClBCy2. The structures of compounds 1, 3, 6 and 9 were confirmed by X-ray diffraction and all displayed a chelate coordination of the guanidinate ligand to the BR′2 fragment, the latter displaying an additional BCy2 attached to the exocyclic N atom. Solutions of compounds 1–4 reached an equilibrium with the aminoboranes Me2NBR′2 [R′ = Nrb (10), Cy (11)] and the corresponding carbodiimides, which was slow at 25 °C. The thermodynamic parameters for these equilibria are also reported. The activation parameters for the equilibrium for compound 1 have been calculated after a kinetic study. Compounds 5–8, with one or two N-aryl fragments bound to a B centre, are more robust and need higher temperatures (80 °C) and prolonged times to give similar carbodiimide de-insertion reactions.

Eleven dimetallic Zn(II)-Ln(III) complexes of the general formula [Zn(µ-L)(µ-OAc)Ln(NO3)2]·CH3CN (Ln(III) = Pr (1), Nd (2), Sm (3), Eu (4), Gd (5), Tb (6), Dy (7), Ho (8), Er (9), Tm (10), Yb (11)) have been prepared in a one-pot reaction from the compartmental ligand N,N'-dimethyl-N,N'-bis(2-hydroxy-3-formyl-5-bromo-benzyl)ethylenediamine (H2L). In all these complexes, the Zn(II) ions occupy the internal N2O2 site whereas the Ln(III) ions show preference for the O4 external site. Both metallic ions are bridged by an acetate bridge, giving rise to triple mixed diphenoxido/acetate bridged Zn(II)Ln(III) compounds. The Nd, Dy, Er and Yb complexes exhibit field induced single-ion magnet (SIM) behaviour, with Ueff values ranging from 14.12 to 41.55 K. The Er complex shows two relaxation processes, but only the second relaxation process with an energy barrier of 21.0 K has been characterized. The chromophoric L(2-) ligand is able to act as an "antenna" group, sensitizing the near-infrared (NIR) Nd(III) and Yb(III)-based luminescence in complexes 2 and 11 and therefore, both compounds can be considered as magneto-luminescent materials. In addition, the Sm(III), Eu(III) and Tb(III) derivatives exhibit characteristic emissions in the visible region.

The reaction of [{RhCl(COD)}2] (COD = 1,5-cyclooctadiene) with L = pyrazole (Hpz), 3(5)-methylpyrazole (Hmpz) or 3,5-dimethylpyrazole (Hdmpz) and PPh2(o-C6H4CHO) (Rh : L : P = 1 : 2 : 1) gives hydridoacyl complexes [RhHCl{PPh2(o-C6H4CO)}(L)2] (1). Stereoselective formation of 1-Hpz and 1-Hmpz with pyrazoles trans to hydrido and phosphorus and hydrogen bond formation with O-acyl and chlorido occur. 1-Hmpz is a mixture of two linkage isomers in a 9 : 1 ratio, with two 5-methylpyrazole ligands or with one 3- and one 5-methylpyrazole ligand, respectively. Fluxional 1-Hdmpz undergoes metallotropic tautomerization and is a mixture of equal amounts of 1a-Hdmpz and 1b-Hdmpz, with hydrido trans to pyrazole or chlorido, respectively. Complexes 1 readily exchange hydrido by chlorido to afford [RhCl2{PPh2(o-C6H4CO)}(L)2] (2-Hpz, 2-Hmpz and 2-Hdmpz) as single isomers with cis chloridos and two N–H⋯Cl hydrogen bonds. The reaction of 1 with PPh3 or PPh2OH affords static [RhHCl{PPh2(o-C6H4CO)}(PPh3)L] (3) or [RhHCl{PPh2(o-C6H4CO)}(PPh2OH)L] (4) respectively with trans P-atoms and pyrazoles forming N–H⋯Cl hydrogen bonds. 3-Hpz and 3-Hmpz contain single species with hydrido cis to chlorido, while 3-Hdmpz is a mixture of equal amounts of 3a-Hdmpz and 3b-Hdmpz. Complexes 4, with an additional O–H⋯O hydrogen bond, selectively contain only the cis-H,Cl species with all the three ligands. The reaction of [{RhCl(COD)}2] with L and PPh2(o-C6H4CHO) (Rh : L : P = 1 : 1 : 2) led to complexes with trans P-atoms, [RhHCl{PPh2(o-C6H4CO)}{PPh2(o-C6H4CHO)-κP}L] (5-Hpz, 5a-Hdmpz and 5b-Hdmpz), at room temperature, and to [RhCl{PPh2(o-C6H4CO)}{PPh2(o-C6H4CHOH)}(Hmpz)] (6-Hmpz) or [RhCl{PPh2(o-C6H4CO)}2L] (7) with hydrogen evolution in refluxing benzene. DFT calculations were used to predict the correct isomers, their ratios and the particular intramolecular hydrogen bonds in these complexes. Single crystal X-ray diffraction analysis was performed on 2-Hpz, 3a-Hdmpz and 7-Hpz. Complexes 1 are efficient homogeneous catalysts (0.5 mol% loading) in the hydrolysis of amine– or ammonia–borane (AB) to generate up to 3 equivalents of hydrogen in the presence of air.

This work reports the syntheses, crystal structures, magnetic properties and DFT calculations of six novel polynuclear NiII compounds [Ni2(μ-HL1)2(μ-N3)]N3·(CH3OH)2·2H2O (1), [Ni2(μ-HL1)2(μ-N3)][Na2Ni2(μ-L1)2(μ-N3)2(CH3OH)(N3)]·4CH3OH (2), [Ni4(μ-L1)2(μ-N3)4(CH3OH)2]·2CH3OH (3), [Na2Ni4(μ-L1)2(μ-OAc)2(μ-N3)4(CH3OH)4]·2CH3OH (4), [Ni4(μ-L1)2(μ-Cl)2(Cl)2] (5), and [Ni3(μ-L1)2(acac)2(H2O)2] (6), with uncommon structures and rare mixed-bridges between NiII ions, which were prepared from the versatile polytopic Mannich base ligand N,N′-dimethyl-N,N′-bis(2-hydroxy-3-methoxy-5-methylbenzyl)ethylenediamine (H2L1). The anionic coligand (azide, chloride, acetate and acetylacetonate) and reaction conditions play crucial roles in determining the final structure of these compounds and consequently their magnetic properties. Compound 1 contains a Ni2 cationic unit with rare di-μ-phenoxido/μ1,1-azide triple mixed bridges whereas complex 2 is made from the same Ni2 cationic unit as 1, cocrystallized with Na2Ni2 neutral units, in which double μ1,1,1-azide bridges connect the NiII and NaI anions. Complexes 3 and 4 are Ni4 complexes with defective dicubane and linear structures, respectively. Complex 3 has two distinct types of mixed bridges, μ-phenoxido/μ1,1,1-azido and μ1,1-azido/μ1,1,1-azido and a double di-μ1,1,1-azido bridge, the latter connecting the face-sharing NiII ions. In 4, rare μ-phenoxido/μ1,1-azide/syn–syn acetate triple mixed bridges connect central and terminal NiII atoms whereas a double μ1,1-azide planar bridging fragment links the central NiII ions. Complex 5 has a defective-dicubane structure with double μ-phenoxido/μ3-chloro mixed bridges and di-μ3-chloro bridges, whereas complex 6 has a bent structure with very uncommon single μ-phenoxido bridges. The analysis of the magnetic properties reveals that in complexes 1–4 all magnetic pathways transmit ferromagnetic interactions leading to S = 2 ground states for 1 and 2 and S = 4 ground states for 3 and 4. In complex 5, the double μ-phenoxido/μ3-chloro mixed bridges and di-μ3-chloro bridges mediate antiferro- and ferromagnetic interactions, respectively, giving rise to a S = 0 ground state. Complex 6 shows antiferromagnetic interactions between the NiII ions through single μ-phenoxido bridging groups, leading to an S = 1 ground state. DFT calculations on the X-ray structures and model compounds were performed to support the magneto-structural data of the above compounds.

The dihydridoirida-β-diketone [IrH2{(PPh2(o-C6H4CO))2H}] (2) has been used as a homogeneous catalyst for the hydrolysis of ammonia- or amine-boranes to generate up to 3 equivalents of hydrogen in the presence of air. When using 0.5 mol% loading of 2, dimethylamine-borane is hydrolysed completely within 8 min at 30 °C and maintains its activity in consecutive runs. Ammonia-borane or tert-butylamine-borane is hydrolysed completely within 32 or 25 min respectively. Triethylamine-borane fails to be hydrolysed. Kinetic studies suggest a sequence of two consecutive first-order reactions, in which an intermediate builds up and finally falls, with the first step being the rate controlling step. ΔH1(‡) are in the range 65-85 kJ mol(-1) and negative values of ΔS1(‡) are obtained. A multinuclear NMR study of the catalyzed reaction shows the formation of a resting state (A) of the active catalyst proposed to be of the hydridodiacyl type [IrH(PPh2(o-C6H4CO))2(solvent)] with a hydride trans to the acyl group. In the absence of substrate a dormant species (B) is formed. By the reaction of hydridoirida-β-diketones with ammonia, the hydridoirida-β-ketoimine [IrHCl{(PPh2(o-C6H4CO))(PPh2(o-C6H4CNH))H}] (3) and the hydridobis(acylphosphane)aminoiridium(III) complex [IrH(PPh2(o-C6H4CO))2(NH3)] (4), with a hydride trans to phosphane, are formed. Aromatic amines such as aniline or anisidines afford cationic [IrH{(PPh2(o-C6H4CO))2H}(C6H4RNH2)]ClO4 (R = H (6); p-MeO (7); o-MeO (8)) hydridoirida-β-diketones with a coordinated amine group trans to the hydride. The dormant species B is proposed to be of the hydridobis(acylphosphine)aminoiridium(III) type with a hydride trans to the amine group.

Four new dinuclear complexes [Ni(μ-L)(μ-OAc)Ni(H2O)2]NO3 (1), Ni(μ-L)(μ-OBz)Ni(H2O)(MeOH)]NO3·3MeOH (2), [Ni(μ-L)(μ-9-An)Ni(H2O)(MeOH)]NO3 (3) and [Ni(μ-L)(μ-OAc)Ni(H2O)(N3)]·CH3OH (4) have been prepared from the compartmental ligand N,N′,N′′-trimethyl-N,N′′-bis(2-hydroxy-3-methoxy-5-methylbenzyl)diethylenetriamine (H2L) and different carboxylate ligands (OBz = benzoate and 9-An = 9-anthracenecarboxylate), and then magnetically and structurally characterized. The X-ray structures of these complexes reveal that the Ni2+ ions are bridged by two phenoxo groups belonging to the L2− ligand and one syn–syn carboxylate group, giving rise to diphenoxocarboxylate triply bridged dinuclear nickel(II) complexes. The syn–syn carboxylate bridging group folds the structure with hinge angles (β) in the range 32–36°. The folding of the structure takes place with a concomitant decrease of the O–Ni–O bridging angle (θ) and an increase of the shift carbon atom directly linked to the phenoxo oxygen atom with respect to the Ni–Ni–O plane in the bridging region (τ angle). All the complexes exhibit ferromagnetic interactions between the slightly distorted octahedral Ni2+ ions. A comparative analysis of the magneto-structural data for 1–4 and other diphenoxocarboxylate bridged complexes clearly show that not only the θ angle, but also the τ and β angles play a significant role in determining the sign and magnitude of the magnetic exchange coupling in these complexes. The ferromagnetic behaviour observed for 1–4 has been justified on the basis of their relatively low θ and high β and τ values, all of them decreasing the antiferromagnetic contribution in complexes 1–4, as well as the countercomplementarity effects between the diphenoxo and carboxylate bridging ligands. DFT theoretical calculations unequivocally demonstrate that the countercomplementarity mechanism is operative in compounds 1–4.

Conventional reactions of the new multidentate ligand 7-amine-1,2,4-triazolo[1,5-a]pyrimidine (7atp, 1) with copper(II) salts lead to four novel multidimensional coordination complexes [Cu(7atp)(mal)(H(2)O)(2)]·H(2)O (2), [Cu(2)(μ-7atp)(4)(H(2)O)(2)](ClO(4))(4)·3H(2)O (3), {[Cu(7atp)(2)(μ-ox)]·3H(2)O}(n) (4) and {[Cu(7atp)(2)(μ-suc)]·2H(2)O}(n) (5), where ox(2-), mal(2-) and suc(2-) mean oxalate, malonate and succinate, respectively. In these compounds, the 7atp ligand coordinates monodentately through its atom N3, except for compound 3, which displays N3-N4 coordination mode, giving rise to all to structures with diverse topologies and dimensionality. Compound 2 is a mononuclear entity, 3 consists of dinuclear species, 4 is a zig-zag chain with oxalate as a bridging ligand and 5 is a succinate-bridged mono-dimensional system. All polynuclear metal complexes show antiferromagnetic interactions of with J values ranging from -0.12 to -49.5 cm(-1). The ligand donor capabilities have been estimated by topological analyses of the electron density (QTAIM) and electron localization function (ELF), obtained by DFT calculations. The compounds are the first structurally characterized copper(II) complexes containing the 7atp ligand.

Conventional reactions of the versatile multidentate ligand 5-methyl-1,2,4-triazolo[1,5-a]pyrimidin-7(4H)-one (HmtpO) with metallic(II) salts lead to three novel multidimensional complexes [Cu(HmtpO)(2)(H(2)O)(3)](ClO(4))(2)·H(2)O (1), {[Cu(HmtpO)(2)(H(2)O)(2)](ClO(4))(2)·2HmtpO}(n) (2) and {[Co(HmtpO)(H(2)O)(3)](ClO(4))(2)·2H(2)O}(n) (3). In each compound, the triazolopyrimidine ligand shows a different and unusual coordination mode, giving rise to structures with diverse topologies and dimensionality. Compound 1 is a monomeric complex, in which HmtpO shows both N3-monodentate and N1,O71-bidentate modes. 2 is a bidimensional framework with the ligand showing a N3,O71 bidentate-bridging mode. The structure of 3 consists of 1D chains, in which HmtpO displays a N1,N3,O71-tridentate-bridging mode. It should be noted that these coordination modes of the HmtpO ligand are unique in the case of compounds 2 and 3. On the other hand, the magnetic properties of the polynuclear complexes 2 and 3 have been studied showing weak ferromagnetic and antiferromagnetic behaviour, respectively.

The double stranded Cu(II)2-metallacyclic complex of formula [Cu2(mbpb)2].2H2O (1) and the triple stranded Ni(II)2-metallacyclic complexes of formula [Ni2(Hmbpb)3]PF6.21H2O (2), [Co(H2O)6][Ni2(mbpb)3)]THF.10H2O (3) and {Ag2(H2O)[Ni2(mbpb)3]}.11H2O (4) (where H2mbpb is the bisbidentate dinucleating bridging ligand 1,3-bis(pyridine-2-carboxamide) benzene) have been synthesised and characterised by single-crystal X-ray diffraction. Within the dinuclear molecules, metal ions are bridged by either fully or semideprotonated bisbidentate ligands, which are coordinated through the pyridine and amidato nitrogen donor atoms. In complex 4 the triple stranded dinuclear Ni2 units are connected to the Ag+ cations through O-amidato bridges and Ag-pi(benzene) interactions to afford a 1D bimetallic chain. Cu2 (1) and Ni2 (2-4) complexes exhibit ferromagnetic coupling between the metal ions through the bridging ligand with J(Cu-Cu) = 21.1 cm(-1) and J(Ni-Ni) in the range of 2.9-3.6 cm(-1), respectively. Amongst copper(II) dinuclear complexes bearing m-phenylenediamidato bridges, complex 1 exhibits the stronger ferromagnetic exchange coupling reported so far. DFT calculations firstly confirm that the spin polarisation mechanism is responsible for the ferromagnetic coupling, and secondly allows us to predict stronger ferromagnetic couplings in Cu(II)(2) complexes with larger tetrahedral distortions of the CuN4 coordination environment.

The [Re2(micro-trz-kappaN1:kappaN2)2(micro-OH)(CO)6]- (trz = 1,2,4-triazolate) organometallic anion reacts with Ag+ to afford a 2D organometallic/coordination network, [Ag[Re2(micro3-trz-kappaN1:kappaN2:kappaN4)2(micro3-OH)(CO)6]]n x 4nCH3OH, which shows dynamic structural changes triggered by solid-liquid guest exchange processes.

The hydrated sodium salt of the novel and versatile 5-(pyrimidyl)tetrazolato ligand (pmtz(-)), Na(pmtz).H(2)O (1), has been prepared in very mild conditions from 2-cyanopyrimidine and NaN(3). Two coordination polymers [Cd(pmtz)(2)]n (2)and [Cd(pmtz)(micro-Cl)(0.5)(micro-N(3))(0.5)(H(2)O)](n)(3), , have been synthesized from (1)under conventional or hydrothermal conditions, respectively, and fully characterized by single-crystal or powder X-ray diffraction methods. Compounds and consist of mono-dimensional polymeric chains, further stabilized by interchain pi-pi stacking and hydrogen bond interactions. Compound , containing octacoordinated Cd ions of crystallographic D(2) symmetry, exhibits neutral (4, 4) layers formed by square units of the metallacalix[4]arene type in 1,3-alternate conformation. Species , and display intense, room temperature, photoluminescence in the solid state.