Preparation and Radical Oligomerization of anFe(II) Complex without Loss of Spin-Crossover Properties

Summary.  11-(4H-1,2,4-Triazol-4-yl)-undecylmethacrylate (1), a new ligand for Fe(II) spin-crossover (SCO) complexes containing a polymerizable group, was synthesized and characterized. The complex [Fe·1 ₃](BF₄)₂ (2) was obtained by reaction of 1 with Fe(BF₄)₂·6H₂O (molar ratio 1/Fe(II) = 3/1) in THF. Complex 2 showed a gradual spin-crossover between 80 and 230 K. The methacrylate units in the ligands of complex 2 could be oligomerized radically in solution (initiator: azoisobutyronitrile) without loss of the spin-crossover behaviour. Received May 30, 2000. Accepted December 10, 2000     

Studies on mono- and dinuclear bisoxime copper complexes with different coordination geometries

Two new mono- and dinuclear Cu(II) complexes, namely [CuL¹]·0.5H₂O (1) and [(Cu₂(L²)₂)(DMF)]·0.5DMF (2) (H₂L¹ = 1,2-bis{[(Z)-(3-methyl-5-oxo-1-phenyl-1H-pyrazolidin-4(4H)-yl)(phenyl)]methylene-aminooxy}ethane; H₂L² = 1,3-bis{[(Z)-(3-methyl-5-oxo-1-phenyl-1H-pyrazolidin-4(4H)-yl)(phenyl)] methyleneaminooxy}propane), have been synthesized and characterized by X-ray crystallography. The unit cell of complex 1 contains two crystallographically independent but chemically identical [CuL¹] molecules and one crystalline water molecule, showing a slightly distorted square-planar coordination geometry and forming a wave-like pattern running along the a-axis via hydrogen bonding and π···π stacking interactions. Complex 2 has a dinuclear structure, comprising two Cu(II) atoms, two completely deprotonated phenolate bisoxime (L²)²⁻ moieties (in the form of enol), and both coordinated and hemi-crystalline DMF molecules. Complex 2 has square-planar and square-pyramidal geometries around the two copper centers, whose basic coordination planes are almost perpendicular and form an infinite three-dimensional supramolecular network structure involving intermolecular C–H···N, C–H···O, and C–H···π(Ph) hydrogen bonding and π···π stacking interactions of neighboring pyrazole rings.     

Synthesis and crystal structures of silver(I) and copper(II) complexes with <Emphasis Type="Italic">p</Emphasis>-xylylene-bridged bipyrazolyl ligands

Two semi-rigid bipyrazolyl ligands, namely 2,3,5,6-tetramethyl-1,4-bis[(3′,5′-dimethyl-1H -pyrazol-4′-yl)methylene]benzene (H₂L) and 2,3,5,6-tetramethyl-1,4-bis[(3′,5′-diphenyl-1H -pyrazol-4′-yl)methylene]benzene (H₂L′), and their Ag(I) and Cu(II) complexes have been prepared and structurally characterized by means of X-ray analysis. In the structures of the metal complexes, namely [Ag₂(H₂L)₂](BF₄)₂·2H₂O (1), [Ag(H₂L)(NO₃)]_n (2), [Cu₂(H₂L)₄(SO₄)₂]·11H₂O (3), and {[Ag(H₂L′)]BF₄}_n (4), the bipyrazoles act as bridging ligands to connect two metal atoms. Complexes 2 and 4 exhibit 1-D polymeric structures, while 1 and 3 are discrete molecules with a rectangular dimer or tetragonal prismatic shapes, respectively. Two different conformations, namely cis and trans, have been observed for these bipyrazolyl ligands.     

Mesogenic and magnetic behavior in cobalt(II) and iron(II) compounds with long alkyl chains

Abstract  

Metal complexes with long alkyl chains [Co(C16-terpy)₃](BF₄)₂ (1), [Fe(C16-terpy)₂](BF₄)₂ (2), [Co(C16-terpy)₂](BPh₄)₂ (3), [Co(C14-terpy)₂](BF₄)₂ (4), and [Fe(C12C10C5-terpy)₂](BF₄)₂ (5) were synthesized and their physical properties characterized, where C16-terpy, C14-terpy, and C12C10C5-terpy are 4′-hexadecyloxy-2,2′:6′,2′′-terpyridine, 4′-tetradecyloxy-2,2′:6′,2′′-terpyridine, and 4′-5′′′-decyl-1′′′-heptadecyloxy-2,2′:6′,2″-terpyridine, respectively. Complexes 1, 2, and 5 exhibited liquid–crystal properties in the temperature ranges of 371–528 K and 466–556 K, and 88–523 K, respectively. Variable-temperature magnetic susceptibility measurements revealed that the Co(II) complexes 1 and 4 exhibited unique spin transitions (T _1/2↓ = 217 K and T _1/2↑ = 260 K for 1 and T _1/2↓ = 250 K and T _1/2↑ = 307 K for 4), so-called ‘reverse spin transition,’ induced by structural phase transitions. Complex 3 exhibited gradual spin-crossover behavior (T _1/2 = 160 K.), and complex 5 exhibited spin transitions (T _1/2↑ = 288 K and T _1/2↓ = 284 K) at the liquid crystal transition temperature. Compounds with multifunction, i.e., magnetic and liquid–crystal properties, are important in the development of molecular materials.     

Solid complexes of iron(II) and iron(III) with rutin

Solid complex compounds of Fe(II) and Fe(III) ions with rutin were obtained. On the basis of the elementary analysis and thermogravimetric investigation, the following composition of the compounds was determined: (1) FeOH(C₂₇H₂₉O₁₆)·5H₂O, (2) Fe₂OH(C₂₇H₂₇O₁₆)·9H₂O, (3) Fe(OH)₂(C₂₇H₂₉O₁₆)·8H₂O, (4) [Fe₆(OH)₂(4H₂O)(C₁₅H₇O₁₂)SO₄]·10H₂O. The coordination site in a rutin molecule was established on the basis of spectroscopic data (UV–Vis and IR). It was supposed that rutin was bound to the iron ions via 4C=O and 5C—oxygen in the case of (1) and (3). Groups 5C–OH and 4C=O as well as 3′C–OH and 4′C–OH of the ligand participate in binding metals ions in the case of (2). At an excess of iron(III) ions with regard to rutin under the synthesis conditions of (4), a side reaction of ligand oxidation occurs. In this compound, the ligands’ role plays a quinone which arose after rutin oxidation and the substitution of Fe(II) and Fe(III) ions takes place in 4C=O, 5C–OH as well as 4′C–OH, 3′C–OH ligands groups. The magnetic measurements indicated that (1) and (3) are high-spin complexes.     

Synthesis, structural characterization and thermal properties of three copper(II) complexes based on aryl hydrazide ligands

The thiosemicarbazide and hydrazide Cu(II) complexes, [Cu₃L₂¹(py)₄Cl₂] (1), [Cu(HL²)py] (2) and [Cu(HL³)py] (3), (H₂L¹ = 1-picolinoylthiosemicarbazide, H₃L² = N′-(2-hydroxybenzylidene)-3-hydroxy-2-naphthohydrazide, H₃L³ = 2-hydroxy-N′-((2-hydroxy-naphthalen-1-yl)methylene)benzohydrazide) have been prepared and characterized through physicochemical and spectroscopic methods as well as X-ray crystallography. Complex 1 has a centrosymmetric structure with –N–N– bridged Cu₃ skeleton. Neighboring molecules are linked into a 3D supermolecular framework by π–π stacking interactions, N–H···Cl and C–H···Cl hydrogen bonds. Complexes 2 and 3 have similar planar structures but different dimers formed by concomitant Cu···N and Cu···O interactions, respectively. Solvent accessible voids with a volume of 391 ?³ are included in the structure of complex 2, indicating that this complex is a potential host candidate. Thermogravimetric analysis shows that the three complexes are stable up to 100 °C.     

Monomeric and polymeric structures derived from 3,3′,4,4′-biphenyltetracarboxylic acid, phenanthroline and metal ions

Under similar hydrothermal synthetic conditions, the reactions of Fe(NO₃)₃/FeCl₂, CuCl₂, NiCl₂, and CdCl₂ with phenanthroline (phen) and 3,3′,4,4′-biphenyltetracarboxylic acid (H₄BPTC) afforded complexes [Fe(phen)₃](H₃BPTC)₂ (1), [Cu(phen)(BPTC)_0.5 · H₂O] · H₂O (2), [Ni₃(phen)₃(BPTC)_1.5(H₂O)₅] · 4H₂O (3) and [Cd(phen)(BPTC)_0.5] · H₂O (4). The short Fe–N distance in the monomeric Fe(phen)₃(H₃ BPTC)₂ (1) shows that the Fe(II) is in a low-spin state. H₃ BPTC⁴⁻ acts as a counter-ion in this complex. In [Cu(phen)(BPTC)_0.5 · H₂O] · H₂O (2), the central Cu(II) is five-coordinated in a square-pyramidal geometry. The ligand BPTC⁴⁻ is centrosymmetric and the four deprotonated carboxylic groups of BPTC⁴⁻ are coordinated to four different copper ions to form a 1D ladder complex indicating a comparatively strong coordination. In [Ni₃(phen)₃(BPTC)_1.5(H₂O)₅] · 4H₂O (3), all nickel(II) atoms are in an octahedral coordination environment. There are two different BPTC⁴⁻ ligands; one is centrosymmetric and the other is asymmetric. Metal ions are linked through fully deprotonated BPTC⁴⁻ ligands to form a 2D metal-organic sheet. [Cd(phen)(BPTC)_0.5] · H₂O (4) has a 3D metal-organic framework. TG, IR, and fluorescence data for the complexes are presented.     

Synthesis and characterization of 2-phenylaniline cyclopalladated complexes

Reaction of the dinuclear complex [Pd{κ2-N2′,C1-2-(2′-NH₂C₆H₄)C₆H₄}Cl]₂ (1) with ligands (L = 4-picoline, sym-collidine) gave the six-membered palladacycles [Pd{κ2-N2′,C1-2-(2′-NH₂C₆H₄)C₆H₄}Cl(L)] (2). The complex 1 reacted with AgX (X = CF₃SO₃, BF₄) and bidentate ligands [L–L = phen (phenanthroline), dppe (bis(diphenylphosphino)ethane), bipy(2,2′-bipyridine) and dppp (bis(diphenylphosphino)propane)] giving the mononuclear orthopalladated complexes [Pd{κ2-N2′,C1-2-(2′-NH₂C₆H₄)C₆H₄}(L–L)] (3) [L–L = phen, dppe, bipy and dppp]. These compounds were characterized by physico-chemical methods, and the structure of [Pd{κ2-N2′,C1-2-(2′-NH₂C₆H₄)C₆H₄}Cl(L)] (L = sym-collidine) was determined by single-crystal X-ray analysis.     

Pivalate Bridged High Spin Manganese(II) and Iron(II) Polymers

Antiferromagnetic Mn(II) polymers of general formula {[L₂Mn(μ-OOCCMe₃)₂][Mn₂(μ-OOCCMe₃)₄]}_n (L = 1,2-phenylenediamine (3) and 4,5-dimethyl-1,2-phenylenediamine (4)) were synthesized from [Mn(μ-OOCCMe₃)₂(HOEt)] _n (1) polymer and arenediamines in MeCN solution. The tetranuclear cluster Fe₄(μ₃-OH)₂(μ-OOCCMe₃)₄(η²-OOCCMe₃)₂(EtOH)₆ (5) was prepared by reacting FeSO₄·7H₂O with KOOCCMe₃ in EtOH and was used as starting pivalate iron(II) agent in further reactions. The thermolysis of 5 in MeCN was shown to result in a ferromagnetic polymer [Fe(μ-OOCCMe₃)₂] _n (6) containing tetrahedral iron(II) atoms. Cluster 5 was found to react with o-phenylenediamine giving rise to ferrimagnetic polymer [Fe(μ-OOCCMe₃)₂(HOEt)]_n (7). The reaction 7 with 2,6-diaminopyridine in MeCN results in binuclear antiferromagnetic complex (2,6-(NH₂)₂C₅H₃N)₂Fe₂(μ-OOCCMe₃)₄· 4MeCN (8). However the reaction of 4,5-dimethyl-1,2-phenylenediamine with polymer 7 yields a polymer {[L₂Fe(μ-OOCCMe₃)₂][Fe₂ (μ-OOCCMe₃)₄]} _n (9), which is an analogue of the manganese polymer 4. All newly synthesized compounds were characterized by the by X-ray diffraction studies and magnetic measurement. Dedicated to Professor Ilya I. Moiseev in recognition of his outstanding contribution to cluster chemistry     

Synthesis, Spectral Characterization and Electrochemical Properties of New vic-dioxime Complexes Bearing Carboxylate

Three new vic-dioxime ligands, [N-(ethyl-4-amino-1-piperidine carboxylate)-phenylglyoxime (L¹H₂), N-(ethyl-4-amino-1-piperidine carboxylate)-glyoxime (L²H₂), and N,N′-bis(ethyl-4-amino-1-piperidine carboxylate)-glyoxime (L³H₂)], and their Co(II) with Cu(II) metal complexes, were synthesized for the first time. Mononuclear complexes of these ligands with a 1:2 metal-ligand ratio were prepared with Co(II) and Cu(II) salts. The BF₂⁺-capped Co(II) and mononuclear complexes of the vic-dioxime were prepared for [Co(L¹·BF₂)₂] and [Co(L²·BF₂)₂]. The ligands act in a polydentate fashion bonding through nitrogen atoms in the presence of a base, as do most vic-dioximes. The cobalt(II) and copper(II) complexes are non-electrolytes as shown by their molar conductivities (Λ_M) in DMF. The structures of the ligands and complexes were determined by elemental analyses, FT-i.r., u.v.–vis., ¹H- and ¹³C-n.m.r. spectra, magnetic susceptibility measurements, and molar conductivity. The comparative electrochemical studies show that the stabilities of the reduced or oxidized species and the electrode potentials of the complexes are affected by the substituents attached on the oxime moieties of the complexes.     

Frontiers of positron and positronium chemistry in condensed media

Our work proves that positron annihilation spectroscopy is an excellent tool to follow the structural changes in chemical species. We present four examples to support the above statement. The sizes of defects in electrodeposited chromium layers were studied and estimated on the basis of positron lifetime spectra decomposed into two components. Vacancies, di-vacancies and vacancy-clusters could be identified in the electrodeposites. The changes of the size distribution of the free volume units in poly(methylmetacrylate) on the dependence of molecular weight and dispersity were described by the correlation between the lifetime ofortho-Ps and the free volume units in polymers. It was found that the free volume is affected by both the molecular weight and dispersity. The effect of dispersity was explained by the sample preparation technique, namely by the application of high pressure. The ortho-para conversion ofortho-Ps was used to follow the partial spin-crossover in [Fe(1-ethyl-1H-tetrazole)₆](BF₄)₂. The spin-crossover temperature was identified to be 105 K. A conformal structural transformation was found in [Zn(1-propyl-1H-tetrazole)₆](BF₄)₂ between 170 and 90 K by positronium lifetime measurement and the role of (BF₄)²⁻ anion, in this transformation, was proved by¹⁹F NMR spectroscopy.     

Mesogenic and magnetic behavior in cobalt(II) and iron(II) compounds with long alkyl chains

Abstract  Metal complexes with long alkyl chains [Co(C16-terpy)₃](BF₄)₂ (1), [Fe(C16-terpy)₂](BF₄)₂ (2), [Co(C16-terpy)₂](BPh₄)₂ (3), [Co(C14-terpy)₂](BF₄)₂ (4), and [Fe(C12C10C5-terpy)₂](BF₄)₂ (5) were synthesized and their physical properties characterized, where C16-terpy, C14-terpy, and C12C10C5-terpy are 4′-hexadecyloxy-2,2′:6′,2′′-terpyridine, 4′-tetradecyloxy-2,2′:6′,2′′-terpyridine, and 4′-5′′′-decyl-1′′′-heptadecyloxy-2,2′:6′,2″-terpyridine, respectively. Complexes 1, 2, and 5 exhibited liquid–crystal properties in the temperature ranges of 371–528 K and 466–556 K, and 88–523 K, respectively. Variable-temperature magnetic susceptibility measurements revealed that the Co(II) complexes 1 and 4 exhibited unique spin transitions (T _1/2↓ = 217 K and T _1/2↑ = 260 K for 1 and T _1/2↓ = 250 K and T _1/2↑ = 307 K for 4), so-called ‘reverse spin transition,’ induced by structural phase transitions. Complex 3 exhibited gradual spin-crossover behavior (T _1/2 = 160 K.), and complex 5 exhibited spin transitions (T _1/2↑ = 288 K and T _1/2↓ = 284 K) at the liquid crystal transition temperature. Compounds with multifunction, i.e., magnetic and liquid–crystal properties, are important in the development of molecular materials. Graphical Abstract  

A series of trinuclear sandwich-like cyanide-bridged iron(III)-manganese(II) complexes: synthesis,crystal structures,and magnetic properties

Four pyridinecarboxamide iron dicyanide building blocks and one Mn(III) compound have been employed to assemble cyanide-bridged heterometallic complexes, resulting in a series of trinuclear cyanide-bridged Fe^III–Mn^II complexes: {[Mn(DMF)₂ (MeOH)₂][Fe(bpb)(CN)₂]₂}·2DMF (1), {[Mn(MeOH)₄][Fe(bpmb)(CN)₂]₂}·2MeOH·2H₂O (2), {[Mn(MeOH)₄][Fe(bpdmb)(CN)₂]₂}·2MeOH·2H₂O (3) and {[Mn(MeOH)₄][Fe(bpClb)(CN)₂]₂}·4MeOH (4) (bpb²⁻ = 1,2-bis(pyridine-2-carboxamido)benzenate, bpmb²⁻ = 1,2-bis(pyridine-2-carboxamido)-4-methyl-benzenate, bpdmb²⁻ = 1,2-bis(pyridine-2-carboxamido)-4,5-dimethyl-benzenate, bpClb²⁻ = 1,2-bis(pyridine-2-carboxamido)-4-chloro-benzenate). Single-crystal X-ray diffraction analysis shows their similar sandwich-like structures, in which the two cyanide-containing building blocks act as monodentate ligands through one of their two cyanide groups to coordinate the Mn(II) center. Investigation of the magnetic properties of these complexes reveals antiferromagnetic coupling between the neighboring Fe(III) and Mn(II) centers through the bridging cyanide group. A best fit to the magnetic susceptibilities of complexes 1 and 3 gave the magnetic coupling constants J = −1.59(2) and −1.32(4) cm⁻¹, respectively.     

基于柔性四羧酸的三个一维/二维/三维Zn(Ⅱ)/Co(Ⅱ)配合物的晶体结构及荧光性质

通过水热/溶剂热合成的方法制备了3个Zn(Ⅱ)/Co(Ⅱ)配合物{[Zn(H₂L)(H₂O)₃]·H₂O·0.5H₄L}_n(1)、{[Co(L)_0.5(4,4'-bpy)]·0.5H₂O}_n(2)和{[Co(L)_0.5(pbmb)(H₂O)]·H₂O}_n(3)(H₄L=5,5'-(hexane-1,6-diyl)-bis(oxy)diisophthalic acid,4,4'-bpy=4,4'-bipyridine,pbmb=1,1'-(1,3-propane)bis-(2-methylbenzimidazole))。结构分析表明配合物1为一维链结构。2为拓扑符号为(6⁴·7·8)(6·7²)的三重穿插网络结构。3是拓扑符号为(4·6²)(4²·6²·8²)的(3,4)-连接的二维网络结构。配合物1呈现出较好的荧光性质。     

Structure and magnetic properties of a dtm-bridged two-dimensional supramolecular complex {[Fe(dtm)2(H2O)2](ClO4)2 · 2H2O} n (dtm = 4,4′-ditriazolemethane)

This work presents the synthesis, crystal structure and magnetic properties of a novel dtm-bridged 2D iron(II) supramolecular complex {[Fe(dtm)₂(H₂O)₂](ClO₄)₂ · 2H₂O} _n (1). The 2D structure of (1) is formed by the incorporation of coordinative linkage and hydrogen-bonding interactions between the oxygen atoms of the anion water cluster [(ClO₄)₂ · 4H₂O]²⁻ and 1D cation complex chain {[Fe(dtm)₂(H₂O)₂]²⁻. The magnetic behavior reveals an antiferromagnetic interaction between Fe(II) ions through hydrogen bonded bridges.     

氰基桥联的Fe2Ni双之字链的合成与磁性

利用四氰基构筑单元和不同位阻的吡啶类配体,合成了3例氰基桥联的Fe₂^ⅢNi^Ⅱ链状化合物。化合物{[Fe（bpy）（CN）₄]₂[Ni（bp）₂]·2H₂O}_n（1）（bpy=2,2''-联吡啶;bp=4-苯基吡啶）,{[Fe（bpy）（CN）₄]₂[Ni（papy）₂]·H₂O}_n（2）（papy=4-（苯基氮烯）吡啶）和{[Fe（bpy）（CN）₄]₂[Ni（azp）]·4H₂O}_n（3）（azp=1,2-二（吡啶-4-基）二氮烯）均为双之字型的链状结构。磁性测试表明化合物1~3均表现为链内的铁磁相互作用。化合物1表现出单链磁体行为,有效能垒为10.9 K。     

两个三维柱层式单一手性配位化合物:合成、结构和性质（英文）

在溶剂热合成条件下得到2个单一手性配位聚合物,即[Cd3((R)-CIA)2(bipy)2.5(H2O)2]·xGuest(1)和[Zn3((R)-CIA)(bmib)2(H2O)2 Cl]·H2O·xGuest(2)((R)-H3CIA=(R)-5-(1-羧基乙氧基)间苯二甲酸,bipy=4,4′-联吡啶,bmib=1,4-双(2-甲基-1H-咪唑-1-基)苯)。X射线单晶结构分析揭示配合物1和2都是柱层式结构的三维框架。从拓扑分析的角度看,配位物1具有(3,3,3,6,6)-连接的网络,拓扑符号为(4.5^2)2(4.8^2)2(42.6^8.8^3.10^2)(4^2.6^8.8^3.9^2)(5.8.9)2,而配合物2是(3,4,4)-连接的网络,拓扑符号为(6·7^2)2(6·7^5)2(6^2·7^4)。此外,对上述配合物的热稳定性、圆二色谱和荧光性质也做了研究。     

Transformations of high spin MnII and FeII polymeric pivalates in reactions with pivalic acid and o-phenylenediamines

The thermolysis and reactions of the polymeric high spin Mn^II and Fe^II complexes [Mn(μ-OOCBu^t)₂(HOEt)]_n (1) and [Fe(μ-OOCBu^t)₂]_n (3) with pivalic acid and o-phenylenediamines 1,2-(NH₂)₂C₆H₂R₂ (R = H or Me) were studied. The synthesis of compound 1 performed with a deficiency of pivalate anions affords the antiferromagnetic chloropivalate polymer { (MeCN)(HOOCBu^t)(H₂O)Mn₅Cl(OH)(OOCBu^t)₈·MeCN}_n. The reaction of 1 with an excess of pivalic acid produces the antiferromagnetic polymer [Mn₄(OOCBu^t)₈(HOOCBu^t)₂]_n. The analogous reaction of pivalic acid with polymer 3 gives the mononuclear complex Fe(η ¹-OOCBu^t)₂(η¹-HOOCBu^t)₄ containing the high spin iron(II) atom as the major product. Study of the reactions of 3 with a deficiency (<1: 1) and an excess (>1: 1) of diamines demonstrated that the polymer {[(η²-(NH₂)₂C₆H₄)₂Fe(μ-OOCBu^t)₂][Fe₂(μ-OOCBu^t)₄] · · 2MeCN}_n is generated as the major product in the former case, whereas the mononuclear complexes Fe(η¹-OOCBu^t)₂[η¹-(NH₂)₂C₆H₄]₄ and Fe(η¹-OOCBu^t)₂[η²-(NH₂)₂C₆H₂Me₂][η¹-(NH₂)₂C₆H₂Me₂]₂ are predominantly obtained in the latter case. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 779–792, May, 2006.     

Synthesis of N-(4′-Benzo[15-crown-5])thiophenoxyphenylaminoglyoxime and its complexes with some transition metals

4-(Chloroacetyl)diphenyl thioether (1) was synthesized from chloroacetyl chloride and diphenyl thioether in the presence of AlCl₃ as catalyst in a Friedel-Crafts reaction. Subsequently, its keto oxime (2) and glyoxime (3) derivatives were prepared. N-(4′-Benzo[15-crown-5]thiophenoxyphenylaminoglyoxime (H₂L) and its sodium chloride complex (H₂L · NaCl) were prepared from 4-(thiophenoxy)chlorophenylglyoxime (3), 4′-aminobenzo[15-crown-5] and sodium bicarbonate or sodium bicarbonate and sodium chloride. Ni(II), Co(II) and Cu(II) complexes of H₂L and H₂L · NaCl have a metal–ligand ratio of 1:2 and the ligand coordinates through the two N atoms, as do most of the vic-dioximes. The BF₂-capped Ni(II) mononuclear complex of the vic-dioxime was prepared. The macrocyclic ligands and their transition metal complexes were characterized on the basis of FT-IR, ¹H NMR, ¹³C NMR spectroscopy and elemental analyses data.     

杂金属杯[4]配位聚合物的合成与表征

合成了4个杂金属杯[4]配位聚合物{[Cd（L）（tpa）]·3H₂O}_n（1）,{[Zn2（L）₂（tpa）₂]·3H₂O}_n（2）,{[Co（L）（oba）]·2DMA·0.5H₂O}_n（3）和{[Zn（L）（oba）]·DMA}_n（4）（L=2-（1H-咪唑基-甲基）-6-（3-（1H-咪唑基-甲基）-5-叔丁基-2-羟基）苄基-4-叔丁基苯酚,H₂tpa=对苯二甲酸,H₂oba=4,4''-二苯醚二甲酸）,并通过元素分析、热重、红外光谱、固态紫外、单晶X射线衍射和粉末X射线衍射对其进行了表征。单晶结构分析表明晶体1是单斜晶系,P2₁/n空间群,而晶体2,3和4均为三斜晶系,P1空间群。化合物1,2,3和4是由0维[M（N₄O₂C₂₉H₃₆）]（M=Zn,Co,Cd）的杂金属杯[4]与配体对苯二甲酸和4,4''-二苯醚二甲酸形成的一维配位聚合物。