Synthesis, structures, and magnetism of copper(II) and manganese(II) coordination polymers with azide and pyridylbenzoates

Three transition-metal coordination polymers with azide and/or carboxylate bridges have been synthesized from 4-(3-pyridyl)benzoic acid (4,3-Hpybz) and 4-(4-pyridyl)benzoic acid (4,4-Hpybz) and characterized by X-ray crystallography and magnetic measurements. Compound 1, [Cu(4,3-pybz)(N(3))](n), consists of 2D coordination networks in which the uniform chains with (μ-EO-N(3))(μ-COO) double bridges are cross-linked by the 4,3-pybz ligands. Compound 2, [Cu(2)(4,4-pybz)(3)(N(3))](n)·3nH(2)O, consists of 2-fold interpenetrated 3D coordination networks with the α-Po topology, in which the six-connected dinuclear motifs with mixed (μ-EO-N(3))(μ-COO)(2) (EO = end-on) triple bridges are linked by the 4,4-pybz spacers. Compound 3, [Mn(4,4-pybz)(N(3))(H(2)O)(2)](n), contains 2D manganese(II) coordination networks in which the chains with single μ-EE-N(3) bridges (EE = end-to-end) are interlinked by the 4,4-pybz ligands, and the structure also features a 2D hydrogen-bonded network in which Mn(II) ions are linked by double triatomic bridges, (μ-EE-N(3))(O-H···N) and (O-H···O)(2). Magnetic studies indicated that the mixed azide and carboxylate bridges in 1 and 2 induce ferromagnetic coupling between Cu(II) ions and that 3 features antiferromagnetic coupling through the EE-azide bridge. In addition, compound 1 exhibits antiferromagnetic ordering below 6.2 K and behaves as a field-induced metamagnet. A magnetostructural survey indicates a general trend that the ferromagnetic coupling through the mixed bridges decreases as the Cu-N-Cu angle increases.     

From simple to complex: topological evolution and luminescence variation in a copper(I) pyridylpyrazolate system tuned via second ligating spacers

By systematically varying the geometric length and electronic properties of the second ligating ligands of halogen (Cl(-), Br(-), and I(-)) and pseudohalogen (CN(-), SCN(-), and N(3)(-)) anions, we synthesized 11 isomeric/isostructural copper(I) complexes: [Cu(2)(L3-3)I](n) (1), [Cu(2)(L4-4)Br](n) (2-Br), [Cu(2)(L4-4)Cl](n) (2-Cl), [Cu(2)(L3-4)(CN)](n) (3), [Cu(2)(L3-3)(CN)](n) (4), [Cu(3)(L4-4)(CN)(2)](n) (5), {[Cu(2)(L4-4)Br](2)·CuBr}(n) (6-Br), {[Cu(2)(L4-4)Cl](2)·CuCl}(n) (6-Cl), [Cu(2)(L4-4)(SCN)](n) (7α-SCN), [Cu(2)(L4-4)(SCN)](n) (7β-SCN), and [Cu(2)(L4-4)(N(3))](n) (7α-N(3)). These structures are based on a series of isomeric pyridylpyrazole ligands, namely, 3,5-bis(3-pyridyl)-1H-pyrazole (HL3-3), 3-(3-pyridyl)-5-(4-pyridyl)-1H-pyrazole (HL3-4), and 3,5-bis(4-pyridyl)-1H-pyrazole (HL4-4), and their structural features range from 1-D (1), 2-D (2), and 3-D noninterpenetration (3), to 3-D 2-fold interpenetration (4 and 5), to 3-D self-catenation (6 and 7), exhibiting a trend from simple to complex with dimension expansion and an interpenetrating degree increase. The five most complex structures (6 and 7) with self-catenated networks are based on 2-fold interpenetrated networks linked via appropriate second ligating spacers (Cl(-), Br(-), SCN(-), and N(3)(-)), representing a strategy to construct self-catenated coordination polymers through cross-linking interpenetrated frameworks. Moreover, these complexes exhibit strong photoluminescence, which is mainly ascribed to Cu(I)-related charge transfers (MLCT, MC, and MMLCT) regulated by the electronic properties of halogen or pseudohalogen. The topological evolution and luminescence variation presented in this work open an avenue to understanding the luminescence origin and the structure-property relationship of luminescent coordination polymers.     

Systematic investigations on magneto-structural correlations of copper(II) coordination polymers based on organic ligands with mixed carboxylic and nitrogen-based moieties

Reaction of copper(II) tetrazolate-5-carboxylate with different neutral N-donor spacer ligands under hydrothermal conditions leads to the formation of five new coordination polymers, [Cu(tzc)(pyz)(0.5)(H(2)O)(2)](n)·H(2)O (1), [Cu(tzc)(pyz)](n) (2), [Cu(tzc)(pym)(H(2)O)](n) (3), [Cu(tzc)(dpe)(0.5)(H(2)O)](n) (4) and [Cu(tzc)(azpy)(0.5)(H(2)O)](n) (5) (tzc = tetrazolate-5-carboxylate, pyz = pyrazine, pym = pyrimidine, dpe = 1,2-di(4-pyridyl)ethylene and azpy = 4,4'-azopyridine). All five structures were characterized by X-ray single-crystal measurements and bulk material can be prepared phase pure in high yields. The crystal structures of the hydrates 1, 3, 4 and 5 show dimeric [Cu(2)(N(tzc)-N(tzc))(2)] building units formed by μ(2)-N1,O1:N2 bridging tzc ligands as the characteristic structural motif. These six-membered entities in 1, 4 and 5 are connected by μ(2)-N,N' bridging N-donor ligands into 1D chains and in 3 into 2D layers. In the crystal structure of compound 2 adjacent Cu(II) cations are connected by μ(2)-N1,O1:N4,O2 bridging tzc ligands into chains, which are further connected by μ(2)-N,N' bridging pyz ligands forming 2D layers. Extensive hydrogen bonds in all compounds play an important role in the construction of their supramolecular networks. Investigations of their thermal properties reveal water release upon heating according to the formation of anhydrates before starting decomposing above 220 °C. Furthermore, the magnetic properties have been studied leading to consistent global antiferromagnetic exchange interactions with coupling constants of J = 3 ± 1 cm(-1) and long-range antiferromagnetic ordering states at lower temperatures.     

Construction of halide-bridged tungsten-copper-sulfide double cubanelike clusters from a new precursor [(Tp*WS2)2(μ-S2)

Treatment of [Et(4)N][Tp*WS(3)] (1) (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate) with 2 equiv of AgSCN in MeCN afforded a novel neutral compound [(Tp*WS(2))(2)(μ-S(2))] (2). Reactions of 2 with excess CuX (X = Cl, Br, I) in MeCN and CH(2)Cl(2) or CHCl(3) formed three neutral W/Cu/S clusters [{Tp*W(μ(3)-S)(3)Cu(3)(μ-Cl)}(2)Cu(μ-Cl)(2)(μ(7)-Cl)(MeCN)](2) (3), [{Tp*W(μ(3)-S)(3)Cu(3)}(2)Br(μ-Br)(2)(μ(4)-Br)(MeCN)] (4), and [{Tp*W(μ(3)-S)(3)Cu(3)}(2){Cu(2)(μ-I)(4)(μ(3)-I)(2)}] (5), respectively. On the other hand, treatment of 2 with CuX (X = Cl, Br) in the presence of Et(4)NX (X = Cl, Br) produced two anionic W/Cu/S clusters [Et(4)N][{Tp*W(μ(3)-S)(3)Cu(3)X}(2)(μ-X)(2)(μ(4)-X)] (6: X = Cl; 7 X = Br). Compounds 2-7 were characterized by elemental analysis, IR, UV-vis, (1)H NMR, electrospray ionization (ESI) mass spectra, and single-crystal X-ray crystallography. The dimeric structure of 2 can be viewed as two [Tp*WS(2)] fragments in which two W atoms are connected by one S(2)(2-) dianion. Compounds 3-7 all possess unique halide-bridged double cubanelike frameworks. For 3, two [Tp*W(μ(3)-S)(3)Cu(3)](2+) dications are linked via a μ(7)-Cl(-) bridge, two μ-Cl(-) bridges, and a [Cu(MeCN)(μ-Cl)(2)](+) bridge. For 4, one [Tp*W(μ(3)-S)(3)Cu(3)(MeCN)](2+) dication and one [Tp*W(μ(3)-S)(3)Cu(3)Br](+) cation are linked via a μ(4)-Br(-) and two μ-Br(-) bridges. For 5, the two [Tp*W(μ(3)-S)(3)Cu(3)](2+) dications are bridged by a linear [(μ-I)(2)Cu(μ(3)-I)(2)Cu(μ-I)(2)](4+) species. For 6 and 7, two [Tp*W(μ(3)-S)(3)Cu(3)X](+) cations are linked by a μ(4)-X(-) and two μ-X(-) bridges (X = Cl, Br). In addition, the third-order nonlinear optical (NLO) properties of 2-7 in MeCN/CH(2)Cl(2) were investigated by using femtosecond degenerate four-wave mixing (DFWM) technique.     

Assembly of trinuclear and tetranuclear building units of Cu2+ towards two 1D magnetic systems: synthesis and magneto-structural correlations

Two new 1D coordination polymers, [Cu(3)(μ(3)-OH)(ppk)(3)(μ-N(CN)(2))(OAc)](n) (1) and {[Cu(4)(pdmH)(2)(pdm)(2)(μ(2)-OH)(H(2)O)]·ClO(4)}(n) (2) based on two different blocking ligands phenyl-2-pyridylketoxime (ppk) and pyridine-2,6-dimethanol (pdmH(2)) have been synthesized and were characterized by X-ray single crystal structural analysis. In compound 1, the hydroxido-bridged trinuclear core, {Cu(3)(μ(3)-OH)(ppk)(3)(OAc)}, acts as secondary building units and are connected by the N(CN)(2)(-) anions resulting in a one dimensional (1D) coordination polymer. The 1D coordination chains undergo π-π interactions giving rise to a 3D supramolecular framework. In compound 2, tetrameric [Cu(4)(pdmH)(2)(pdm)(2)(H(2)O)](2+) cores are linked via hydroxido groups forming a zigzag 1D coordination chain where non-coordinated ClO(4)(-) ions are intercalated between the chains. Variable temperature magnetic susceptibility study of suggests that Cu(II) ions in the trinuclear Cu(3)(μ(3)-OH) cores are antiferromagnetically coupled with J = -459.7 cm(-1) and g = 2.11 and the trinuclear cores are further weakly coupled antiferromagnetically (zj' = -5.25 cm(-1)) through the N(CN)(2)(-) bridging ligand. Investigation of the magnetic properties of reveals that Cu(II) ions are coupled antiferromagnetically in the tetranuclear core with J = -27.1 cm(-1) and g = 2.17; the Cu(II)(4) building units are further coupled antiferromagnetically with zj' = -9.65 cm(-1). The experimental magnetic behaviours of 1 and 2 are correlated by first principle DFT calculations which provide a qualitative understanding of the origin of antiferromagnetic interactions in both cases.     

Construction of a porous homochiral coordination polymer with two types of Cu(n)I(n) alternating units linked by quinine: a solvothermal and a mechanochemical approach

The polymer network: The reaction of quinine (QN) with CuI under solvothermal, as well as liquid-assisted grinding, conditions afforded a unique 1D homochiral coordination polymer {[Cu(4)(μ(3)-I)(4)(QN)(2)][Cu(3)(μ(3)-I)(2)(μ(2)-I)(QN)(2)](2)}(n), containing both triangular Cu(3)I(3) and cubane Cu(4)I(4) clusters as connecting nodes (see scheme). Van der Waals interactions between the adjacent 1D polymer chains lead to an extended quasi-honeycomb homochiral pillared 3D network with solvent-free 1D channels.     

Assembly of bicyclic or monocyclic clusters from [(η5-C5Me5)2Mo2(μ3-S)4(CuMeCN)2]2+ with tetraphosphine or N,P mixed ligands: syntheses, structures and enhanced third-order NLO performances

Reactions of the preformed cluster [(η(5)-C(5)Me(5))(2)Mo(2)(μ(3)-S)(4)Cu(2)(MeCN)(2)](ClO(4))(2) (1) with two tetraphosphine ligands, 1,4-N,N,N',N'-tetra(diphenylphosphanylmethyl)benzene diamine (dpppda) and N,N,N',N'-tetra(diphenylphosphanylmethyl)ethylene diamine (dppeda), produced two bicyclic clusters {[(η(5)-C(5)Me(5))(2)Mo(2)(μ(3)-S)(4)Cu(2)](2)(L)}(ClO(4))(4) (3: L = dpppda; 4: L = dppeda). Analogous reactions of 1 or [(η(5)-C(5)Me(5))(2)Mo(2)(μ(3)-S)(4)Cu(2)(MeCN)(2)](PF(6))(2) (2) with two N,P mixed ligands, N,N-bi(diphenylphosphanylmethyl)-2-aminopyridine (bdppmapy) and N-diphenylphosphanylmethyl-4-aminopyridine (dppmapy), afforded two monocyclic clusters {[(η(5)-C(5)Me(5))(2)Mo(2)(μ(3)-S)(4)Cu(2)](2)(L)(2)}X(4) (5: L = bdppmapy, X = ClO(4); 6: L = dppmapy, X = PF(6)). Compounds 3-6 were fully characterized by elemental analysis, IR spectra, UV-vis spectra, (1)H and (31)P{(1)H} NMR spectra, ESI-MS and single-crystal X-ray crystallography. In the tetracations of 3-6, two cubane-like [Mo(2)(μ(3)-S)(4)Cu(2)] cores are linked either by one dpppda or dppeda bridge to form a bicyclic structure or by a pair of bdppmapy or dppmapy bridges to afford a monocyclic structure. The third-order nonlinear optical (NLO) properties of 1 and 3-6 in MeCN were also investigated by femtosecond degenerate four-wave mixing (DFWM) technique with a 50 fs pulse width at 800 nm. Compounds 3-6 exhibited enhanced third-order NLO performances relative to that of 1.     

Activation and amplification of the third-order NLO and luminescent responses of a precursor cluster by a supramolecular approach

Solvothermal reactions of [Et(4)N][Tp*WS(3)(CuCl)(3)] (1) (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate) with CuCN and KCu(CN)(2) afforded two [Tp*WS(3)Cu(3)]-based coordination polymers [Tp*WS(3)Cu(3)(μ(3)-DMF){Cu(CN)(3)}](2) (2) and K[Tp*WS(3)Cu(3)(μ(3)-DMF){Cu(2)(CN)(4.5)}](2) (3). The third-order NLO and PL responses of 1 were activated and greatly amplified through its assembly via the [Cu(CN)(3)](2-) and [Cu(4)(CN)(9)](5-) species in 2 and 3.     

Thiodiacetate-manganese chemistry with N ligands: unique control of the supramolecular arrangement over the metal coordination mode

Compounds based on the Mn-tda unit (tda=S(CH(2)COO)(2)(-2) ) and N co-ligands have been analyzed in terms of structural, spectroscopic, magnetic properties and DFT calculations. The precursors [Mn(tda)(H(2)O)](n) (1) and [Mn(tda)(H(2)O)(3)]·H(2)O (2) have been characterized by powder and X-ray diffraction, respectively. Their derivatives with bipyridyl-type ligands have formulas [Mn(tda)(bipy)](n) (3), [{Mn(N-N)}(2)(μ-H(2)O)(μ-tda)(2)](n) (N-N=4,4'-Me(2)bipy (4), 5,5'-Me(2)bipy, (5)) and [Mn(tda){(MeO)(2)bipy}·2H(2)O](n) (6). Depending on the presence/position of substituents at bipy, the supramolecular arrangement can affect the metal coordination type. While all the complexes consist of 1D coordination polymers, only 3 has a copper-acetate core with local trigonal prismatic metal coordination. The presence of substituents in 4-6, together with water co-ligands, reduces the supramolecular interactions and typical octahedral Mn(II) ions are observed. The unicity of 3 is also supported by magnetic studies and by DFT calculations, which confirm that the unusual Mn coordination is a consequence of extended noncovalent interactions (π-π stacking) between bipy ligands. Moreover, 3 is an example of broken paradigm for supramolecular chemistry. In fact, the desired stereochemical properties are achieved by using rigid metal building blocks, whereas in 3 the accumulation of weak noncovalent interactions controls the metal geometry. Other N co-ligands have also been reacted with 1 to give the compounds [Mn(tda)(phen)](2)·6H(2)O (7) (phen=1,10-phenanthroline), [Mn(tda)(terpy)](n) (8) (terpy=2,2':6,2'-terpyridine), [Mn(tda)(pyterpy)](n) (9) (pyterpy=4'-(4-pyridyl)-2,2':6,2'-terpyridine), [Mn(tda)(tpt)(H(2)O)]·2H(2)O (10) and [Mn(tda)(tpt)(H(2)O)](2)·2H(2)O (11) (tpt=2,4,6-tris(2-pyridyl)-1,3,5-triazine). Their identified mono-, bi- or polynuclear structures clearly indicate that hydrogen bonding is variously competitive with π-π stacking.     

Synthesis, structural characterization and luminescent properties of a series of Cu(I) complexes based on polyphosphine ligands

A series of Cu(I) complexes with a [Cu(NN)(PP)](+) moiety, [Cu(phen)(pba)](BF(4)) (1a), [Cu(2)(phen)(2)(pbaa)](BF(4))(2) (2a), [Cu(2)(phen)(2)(pnaa)](BF(4))(2) (3a), [Cu(2)(phen)(2)(pbbaa)](BF(4))(2) (4a), [Cu(dmp)(pba)](BF(4)) (1b), [Cu(2)(dmp)(2)(pbaa)](BF(4))(2) (2b), [Cu(2)(dmp)(2)(pnaa)](BF(4))(2) (3b) and [Cu(2)(dmp)(2)(pbbaa)](BF(4))(2) (4b) (phen = 1,10-phenanthroline, dmp = 2,9-dimethyl-1,10-phenanthroline, pba = N,N-bis((diphenylphosphino)methyl)benzenamine, pbaa = N,N,N',N'-tetrakis((diphenylphosphino)methyl)benzene-1,4-diamine, pnaa = N,N,N',N'-tetrakis((diphenylphosphino)methyl)naphthalene-1,5-diamine and pbbaa = N,N,N',N'-tetrakis((diphenylphosphino)methyl)biphenyl-4,4'-diamine), were rationally designed and synthesized. These complexes were characterized by (1)H and (31)P NMR, electrospray mass spectrometry, elemental analysis and X-ray crystal structure analysis. Introduction of different central arene spacers (phenyl, naphthyl, biphenyl) into ligands, resulting in the size variation of these complexes, aims to tune the photophysical properties of the complexes. Each Cu(I) ion in these complexes adopts a distorted tetrahedral geometry constructed by the chelating diimine and phosphine groups. Intermolecular C-H···π and/or π···π interactions are involved in the solid states. The dmp-containing complex exhibits better emission relative to the corresponding phen complex due to the steric encumbrance of bulky alkyl groups. Furthermore, for complexes with identical diimine but different phosphine ligands, the tendency of increased emission lifetime as well as blue-shifted emission in the solid state follows with the decrease in size of complexes. Intermolecular C-H···π interactions have an influence on the final solid state photophysical properties through vibrationally relaxed non-radiative energy transfer in the excited state. Smaller-sized complexes show better photophysical properties due to less vibrationally relaxed behavior related to flexible C-H···π bonds. Nevertheless, the tendency for increased quantum yield and emission lifetime, as well as blue-shifted emission in dilute solution goes with the increase in size of complexes. The central arene ring (phenyl, naphthyl or biphenyl) has an influence on the final photophysical properties. The larger the π-conjugated extension of central arene ring is, the better the photophysical properties of complex are. The rigid and large-sized complex 3b, with a high quantum yield and long lifetime, is the best luminophore among these complexes.     

Three-dimensional networks based on trinuclear motifs with tricomponent azide-carboxylate-tetrazolate cobridges: synthesis, structure and magnetic properties

Two 3D coordination polymers of Mn(II) with azide and bifunctional zwitterionic ligands bearing both carboxylate and tetrazolate groups, 1-(carboxylatomethyl)-3-(5-tetrazolato)pyridinium (L(1)) and 1-(carboxylatoethyl)-4-(5-tetrazolato)pyridinium (L(2)), were synthesized, and structurally and magnetically characterized. They are formulated as [Mn(3)(L(1))(2)(N(3))(4)(H(2)O)(2)](n)·4nH(2)O (1) and [Mn(3)(L(2))(2)(N(3))(4)(H(2)O)(3)](n)·3.5nH(2)O (2). In both compounds, octahedral Mn(II) ions are linked by the mixed (μ(2)-EO-N(3))(μ(2)-syn,syn-COO)(μ(2)-N(2),N(3)-CN(4)) (CN(4) = tetrazolate and EO = end-on) triple bridges to give anionic linear trinuclear motifs. The motifs are connected through EE-N(3) (EE = end-to-end) bridges to give layers and chains in 1 and 2, respectively, and the cationic pyridinium spacers serve to interlink the layers or chains into three-dimensional frameworks with the α-Po and CdSO(4)-type topology, respectively. Magnetic studies demonstrated that the magnetic interactions within and between the trinuclear motifs, through the tricomponent and EE-N(3) bridges, respectively, are both antiferromagnetic in both compounds.     

2-Benzoylpyridine thiosemicarbazone as a novel reagent for the single pot synthesis of dinuclear Cu(I)-Cu(II) complexes: formation of stable copper(II)-iodide bonds

2-Benzoylpyridine thiosemicarbazone {R(1)R(2)C(2)=N(2)·N(3)H-C(1)(=S)-N(4)H(2), R(1) = py-N(1), R(2) = Ph; Hbpytsc} with copper(I) iodide in acetonitrile-dichloromethane mixture has formed stable Cu(II)-I bonds in a dark green Cu(II) iodo-bridged dimer, [Cu(2)(II)(μ-I)(2)(η(3)-N(1),N(2),S-bpytsc)(2)] 1. Copper(I) bromide also formed similar Cu(II)-Br bonds in a dark green Cu(II) bromo-bridged dimer, [Cu(2)(II)(μ-Br)(2)(η(3)-N(1),N(2),S-bpytsc)(2)] 3. The formation of dimers 1 and 3 appears to be due to a proton coupled electron transfer (PCET) process wherein copper(I) loses an electron to form copper(II), and this is accompanied by a loss of -N(3)H proton of Hbpytsc ligand resulting in the formation of anionic bpytsc(-). When copper(I) iodide was reacted with triphenylphosphine (PPh(3)) in acetonitrile followed by the addition of 2-benzoylpyridine thiosemicarbazone in dichloromethane (Cu?:?PPh(3)?:?Hbpytsc in the molar ratio 1:1:1), both Cu(II) dimer 1 and an orange Cu(I) sulfur-bridged dimer, [Cu(2)(I)I(2)(μ-S-Hbpytsc)(2)(PPh(3))(2)] 2 were formed. Copper(I) bromide with PPh(3) and Hbpytsc also formed Cu(II) dimer 3 and an orange Cu(I) sulfur-bridged dimer, [Cu(2)(I)Br(2)(μ-S-Hbpytsc)(2)(PPh(3))(2)] 4. While complexes 2 and 4 exist as sulfur-bridged Cu(I) dimers, 1 and 3 are halogen-bridged. The central Cu(2)S(2) cores of 2 and 4 as well as Cu(2)X(2) of 1 (X = I) and 3 (X = Br) are parallelograms. One set of Cu(II)-I and Cu(II)-Br bonds are short, while the second set is very long {1, Cu-I, 2.565(1), 3.313(1) ?; 3, Cu-Br, 2.391(1), 3.111(1) ?}. The Cu···Cu separations are long in all four complexes {1, 4.126(1); 2, 3.857(1); 3, 3.227(1); 4, 3.285(1) ?}, more than twice the van der Waals radius of a Cu atom, 2.80 ?. The pyridyl group appears to be necessary for stabilizing the Cu(II)-I bond, as this group can accept π-electrons from the metal.     

WS4Cu3I2]- and [WS4Cu4]2+ secondary building units formed a metal-organic framework: large tubes in a highly interpenetrated system

A 3D metal-organic framework, {[WS(4)Cu(4)(dpbp)(4)](2+)·[WS(4)Cu(3)(dpbp)(2)I(2)](-)·I(-)}(n)·xSolvent, [dpbp = 4,4'-di(4-pyridyl)biphenyl] with an unprecedent 8-fold non-equivalent interpenetration mode is presented, which contains four anionic and four cationic frameworks formed by tetranuclear [WS(4)Cu(3)I(2)](-) and pentanuclear [WS(4)Cu(4)](2+) SBUs with long dpbp ligands. Large rhombus-shaped tubes with diagonal dimensions of ~20 × 10 ? are formed in spite of high interpenetration.     

Novel single-crystal-to-single-crystal anion exchange and self-assembly of luminescent d(10) metal (Cd(II), Zn(II), and Cu(I)) complexes containing C(3)-symmetrical ligands

Ligands L1 and L2' (L1=N,N',N'-tris(4-pyridyl)trimesic amide, L2'=N,N',N'-tris(3-pyridinyl)-1,3,5-benzenetricarboxamide) belonging to an interesting family of tripyridyltriamides with C(3)-symmetry have been utilized to construct 3D porous or hydrogen-bonded frameworks. Through a novel single-crystal-to-single-crystal anion-exchange process, [Cd(L1)(2)(ClO(4))(2)](n) (1c) can be obtained from [Cd(L1)(2)Cl(2)](n) (1b) in the presence of ClO(4)(-) anions. This anion-exchange process is highly selective and only the substitution of Cl(-) by ClO(4)(-) or PF(6)(-) could be realized; Cl(-) was found not to be substituted by BPh(4)(-). This demonstrates that the exchange process depends on the size of the anions in relation to the size of the cavities in the host material (ca. 7.5 A). In addition, the anion-exchange properties of 1 b have also been investigated by means of powder X-ray diffraction (PXRD), elemental analysis (EA), and infrared absorption spectroscopy (IR). Structurally, [Zn(L1)(NO(3))(2)](n)(2) consists of a 2D coordination network with five-coordinate Zn(II) ions. Surprisingly, different trigonal-bipyramidal Zn(II) ions propagate to form distinct respective sheet structures, A and B, which are packed in an A-B-A-B manner in the crystal lattice, and these are hydrogen-bonded to give a 3D extended framework. The molecular structure of [CuI(L2')](n)(3) shows that the Cu(I) ion adopts a distorted tetrahedral geometry, and 3 also forms a 2D coordination network. Significantly, this 2D coordination network is further assembled into a remarkable 3D homochiral framework through triple hydrogen bonding and pi...pi interactions. All of these 3D coordination polymers and/or hydrogen-bonded frameworks are luminescent in the solid state, and their solid-state luminescent properties have been investigated at room temperature and/or at 77 K.     

From achiral ligands to chiral coordination polymers: spontaneous resolution, weak ferromagnetism, and topological ferrimagnetism

Using the achiral diazine ligands bearing two bidentate pyridylimino groups as sources of conformational chirality, five azido-bridged coordination polymers are prepared and characterized crystallographically and magnetically. The chirality of the molecular units is induced by the coordination of the diazine ligands in a twisted chiral conformation. The use of L(1) (1,4-bis(2-pyridyl)-1-amino-2,3-diaza-1,3-butadiene) and L(2) (1,4-bis(2-pyridyl)-1,4-diamino-2,3-diaza-1,3-butadiene) induces spontaneous resolution, yielding conglomerates of chiral compounds [Mn(3)(L(1))(2)(N(3))(6)](n) (1) and [Mn(2)(L(2))(2)(N(3))(3)](n)(ClO(4))(n).nH(2)O (2), respectively, where triangular (1) or double helical (2) chiral units are connected into homochiral one-dimensional (1D) chains via single end-to-end (EE) azido bridges. The chains are stacked via hydrogen bonds in a homochiral fashion to yield chiral crystals. When L(3) (2,5-bis(2-pyridyl)-3,4-diaza-2,4-hexadiene) is employed, a partial spontaneous resolution occurs, where binuclear chiral units are interlinked into fish-scale-like homochiral two-dimensional (2D) layers via single EE azido bridges. The layers are stacked in a heterochiral or homochiral fashion to yield simultaneously a racemic compound, [Mn(2)(L(3))(N(3))(4)](n) (3a), and a conglomerate, [Mn(2)(L(3))(N(3))(4)](n).nMeOH (3b). On the other hand, the ligand without amino and methyl substituents (L(4), 1,4-bis(2-pyridyl)-2,3-diaza-1,3-butadiene) does not induce spontaneous resolution. The resulting compound, [Mn(2)(L(4))(N(3))(4)](n) (4), consists of centrosymmetric 2D layers with alternating single diazine, single EE azido, and double end-on (EO) azido bridges, where the chirality is destroyed by the centrosymmetric double EO bridges. These compounds exhibit very different magnetic behaviors. In particular, 1 behaves as a metamagnet built of homometallic ferrimagnetic chains with a unique "fused-triangles" topology, 2 behaves as a 1D antiferromagnet with alternating antiferromagnetic interactions, 3a and 3b behave as spin-canted weak ferromagnets with different critical temperatures, and 4 also behaves as a spin-canted weak ferromagnet but exhibits two-step magnetic transitions.     

Syntheses, characterization, and magnetic studies of copper(II) complexes with the ligand N,N,N',N'-tetrakis(2-pyridylmethyl)-1,3-benzenediamine (1,3-tpbd) and its phenol derivative 2,6-bis[bis(2-pyridylmethyl)amino]-p-cresol] (2,6-Htpcd)

The copper(II) complexes [Cu(4)(1,3-tpbd)(2)(H(2)O)(4)(NO(3))(4)](n)(NO(3))(4n)·13nH(2)O (1), [Cu(4)(1,3-tpbd)(2)(AsO(4))(ClO(4))(3)(H(2)O)](ClO(4))(2)·2H(2)O·0.5CH(3)OH (2), [Cu(4)(1,3-tpbd)(2)(PO(4))(ClO(4))(3)(H(2)O)](ClO(4))(2)·2H(2)O·0.5CH(3)OH (3), [Cu(2)(1,3-tpbd){(PhO)(2)PO(2)}(2)](2)(ClO(4))(4) (4), and [Cu(2)(1,3-tpbd){(PhO)PO(3)}(2)(H(2)O)(0.69)(CH(3)CN)(0.31)](2)(BPh(4))(4)·Et(2)O·CH(3)CN (5) [1,3-tpbd = N,N,N',N'-tetrakis(2-pyridylmethyl)-1,3-benzenediamine, BPh(4)(-) = tetraphenylborate] were prepared and structurally characterized. Analyses of the magnetic data of 2, 3, 4, and [Cu(2)(2,6-tpcd)(H(2)O)Cl](ClO(4))(2) (6) [2,6-tpcd = 2,6-bis[bis(2-pyridylmethyl)amino]-p-cresolate] show the occurrence of weak antiferromagnetic interactions between the copper(II) ions, the bis-terdentate 1,3-tpbd/2,6-tpcd, μ(4)-XO(4) (X = As and P) μ(1,2)-OPO and μ-O(phenolate) appearing as poor mediators of exchange interactions in this series of compounds. Simple orbital symmetry considerations based on the structural knowledge account for the small magnitude of the magnetic couplings found in these copper(II) compounds.     

Structural and magnetic properties of three novel complexes with the versatile ligand 5-methyl-1,2,4-triazolo[1,5-a]pyrimidin-7(4H)-one

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.     

Self-assembly and characterization of copper 3,4-pyridinedicarboxylate complexes based on a variety of polynuclear hydroxo clusters

Self-assembly of copper(ii) ion, 3,4-pyridinedicarboxylate (PDC), and 1,10-phenanthroline (phen) under basic conditions at 100 °C affords four PDC linked copper(ii) complexes, [Cu(4)(μ(2)-OH)(3)(μ(3)-OH)(PDC)(phen)(4)](n)·n(PDC)·11.5 nH2O (1), [Cu(4)(μ(2)-OH)(2)(μ(3)-OH)(2)(PDC)(phen)(4)](n)·n(PDC)· 11.5 nH(2)O (2), [Cu(8)(μ(2)-OH)(2)(μ(3)-OH)(6)(PDC)(2)(phen)(8)]·2(PDC)·23 H(2)O (3), and [Cu(3.5)(μ(2)-OH)(3) (PDC)(2)(phen)](n) (4). 1-4 are copper hydroxo complexes, and 1, 2 and 3 co-crystallized from the one-pot reaction. X-ray single crystal diffraction analyses indicate that complexes 1 and 2 are linkage isomers and contain tetranuclear copper cluster cores with different geometry, and that PDC links the cluster core to form a one-dimensional chain. Complex 3 is a discrete step-like octanuclear copper hydroxo cluster complex. The involvement of hydroxo and phen in the coordination makes some coordination sites of PDC idle, which leads to rich hydrogen bonds and π-π interactions in complexes 1, 2 and 3. Complex 4 contains two types of copper hydroxo cluster cores: chair-like tetranuclear and linear trinuclear units, and the cluster cores are linked by PDC to a double-layer metal-organic framework. Magnetic properties of 1, 3 and 4 were investigated. The results reveal that complexes 3 and 4 exhibit strong antiferromagnetic interactions whereas ferromagnetic coupling is predominant for complex 1. The magnetic properties are analyzed in connection with their structures.     

Manganese(II) coordination polymers with mixed azide and pyridylbenzoate N-oxide ligands: structures and magnetism

Two novel Mn(II) coordination polymers with azide and 4-(4-pyridyl)benzoic acid N-oxide (4,4-Hopybz) were synthesized and structurally and magnetically characterized. They are formulated as {[Mn(2)(4,4-opybz)(2)(N(3))(2)(H(2)O)(2)]·H(2)O}(n) (1) and {[Mn(4)(4,4-opybz)(5)(N(3))(H(2)O)(8)](N(3))(2)·2H(2)O}(n) (2). Compound 1 contains 2D coordination layers in which the infinite Mn(II) chains with alternating (μ-EO-N(3))(2)(μ-COO) (EO = end-on) and (μ-COO)(μ-O) bridges are interlinked by the backbones of the organic ligands. Compound 2 is a 3D metal-organic framework in which the unique linear tetranuclear clusters with (μ-EO-N(3))(μ-COO) and (μ-COO)(μ-O) bridges are cross-linked by organic backbones, and it represents a new example of the rare 8-connected self-catenated 3D net with the point symbol 4(16)·6(12). Magnetic analyses on the compounds have been performed in the classical-spin approximation, revealing that all the above-mentioned mixed bridging motifs induce weak antiferromagnetic interactions between Mn(II) ions.     

A dinuclear extension to constrained heteroleptic Cu(I) systems

This article reports the synthesis and optical properties of three dinuclear, cationic copper complexes [Cu(2)(μ-dppm)(2)(μ-L)](NO(3))(2) (dppm diphenyldiphosphinomethane, L: L(A) 3,6-bis(2-pyridyl)-4,5-diphenyl-pyridazine, L(B) 3,6-bis(2-pyridyl)-4,5-di(4-pyridyl)-pyridazine and L(C) 3,6-bis(2-pyridyl)-8,9-diazafluoranthene). These were formed on the reaction of [Cu(μ-dppm)(NO(3))](2) with a series of N-donor (bppn) ligands L. The single crystal X-ray structures of [Cu(2)(μ-dppm)(2)(μ-L)](NO(3))(2)·CH(2)Cl(2) were determined and revealed that in both, the two copper atoms are held by three bridging ligands, two dppm ligands and one bppn ligand acting as a tetradentate bridge. The absorption spectra of the complexes present a MLCT [Cu → π*(N(∧)N)] band in the λ 370-425 nm region. These new complexes exhibit red-orange MLCT-based emission in the solid-state with lifetimes in the microsecond range. In oxygen-free dichloromethane solution, the complex [Cu(2)(μ-dppm)(2)(μ-L(C))](2+) has a long lifetime of 22.8 μs. The long emission lifetimes are attributed to a rigid conformation that precludes the possible distortion of the copper in the excited state.