Synthesis and crystal structure of [Na2(μ-H2O)(H2O)CB[5]]Cl2 · 6H2O, [Na3(μ-H2O)4(H2O)4(CNPy@CB[6])]Cl3 · 8H2O, and [Rb2(μ-H2O)2(CNPy@CB[6])]Cl · 8H2O

The chain coordination polymers [Na₂(μ-H₂O)(H₂O)CB[5]]Cl₂ · 6H₂O (I), [Na₃(μ-H₂O)₄(H₂O)₄(CNPy@CB[6])]Cl₃ · 8H₂O (II), and [Rb₂(μ-H₂O)₂(CNPy@CB[6])]Cl₂ · 8H₂O (III) were prepared by heating (110°C) of a mixture of sodium or rubidium chloride, cucurbit[n]uril (CB[n], where n = 5, 6), 4-cyanopyridine, and water. According to X-ray diffraction data, binding of polynuclear cations with CB[n] in I–III occurs through coordination of the oxygen atoms of the cucurbit[n]uril portals to alkali metal atoms. Complexes I–III of the above composition isolated to the solid phase as supramolecular compounds with CB[n] were structurally characterized for the first time.     

New lanthanide-based complexes constructed from cucurbit[6]uril: Synthesis,structures and properties

Three lanthanide-based complexes, {Gd₂(H₂O)₁₀(CB[6])₂}·CB[6]·6Cl·12H₂O (1), {[Gd₂(H₂O)₈CB[6]₂]·(CuCl₄)·4Cl·46H₂O}_n (2), and {Dy₂(NO₃)₂(H₂O)₁₀(CB[6])}·4NO₃·14H₂O (3) (CB[6] = cucurbit[6]uril), were prepared with cucurbit[6]uril (CB[6]). These complexes were characterized by single-crystal X-ray diffraction, elemental analysis, FT-IR spectroscopy, UV–Vis spectroscopy, thermogravimetric analysis and magnetization measurements. Crystallographic results showed that 1 and 3 are dinuclear and crystallize in the triclinic space group Pī, whereas 2 is a 1-D zigzag supramolecular chain that crystallizes in the monoclinic system in C2/c. The results indicated that temperature has a big effect on the supramolecular assemblies and a different structure inducer also leads to the formation of different coordination polymers. Frequency dependence in the ac susceptibility signals was observed in 3.     

Synthesis, crystal structures, and properties of [Ca(H2O)2(Dmf@CB[6])(Bdc)] · DMF · 4H2O and [Ca(H2O)3(Dmf@CB[6])]Cl2 · 2H2O

Complexes [Ca(H₂O)₂(Dmf@CB[6])(Bdc)] · DMF · 4H₂O (I) and [Ca(H₂O)₃(Dmf@CB[6])]Cl₂ · 2H₂O (II) are synthesized by the heating (95°C) of a mixture of calcium chloride and cucurbit[6]uril (CB[6]) in a mixture of dimethylformamide (DMF) and water with the addition of terephthalic acid (H₂Bdc) in the case of complex I or triethylamine for complex II. The compounds are characterized by X-ray diffraction analysis, IR spectroscopy, and thermogravimetric and elemental analyses. The luminescence spectra are also recorded. According to the X-ray diffraction data, the calcium atom is coordinated by the oxygen atoms of the cucurbit[6]uril molecule, water molecules, and terephthalate anion (for I). The internal cavity of the cavitand is occupied by DMF.     

H3BTC‐Induced Supramolecular Assembly Based on Cucurbit[6]uril: Possible Application for Sensing Small Molecules

The compound 2[Ca(H₂O)₃ (DMF@CB[6])] · 2(BTC) · 15H₂O ( CCUT ‐ 102 , CB[6] = cucurbit[6]uril; H₃BTC = 1,3,5‐benzenetricarboxylic acid) was synthesized using the approach of organic guest‐induced formation of polymers or frameworks based on the coordination of metal ions and cucurbit[n]urils. The compound was characterized by X‐ray diffraction analysis, PXRD, IR spectroscopy, thermogravimetric and elemental analyses. According to the X‐ray diffraction data, the calcium atom is coordinated by the oxygen atoms of the CB[6] molecule, water molecules, and N ,N‐dimethylformamide (DMF). The internal cavity of CB[6] is occupied by DMF. Each H₃BTC molecule interacts the CB[6] molecules through π?π interactions between aromatic rings of H₃BTC and the rings of CB[6]. The luminescence behaviors and sensing properties of CCUT ‐ 102 in different solvents were also studied.     

Inclusion compounds of cucurbit[8]uril with noble metal polyamine complexes

Inclusion compounds of the macrocyclic cavitand cucurbit[8]uril (CB[8]) with the ruthenium(iii) bis(ethylenediamine) complex {trans-[Ru(en)₂Cl₂]@CB[8]}Cl·27.5H₂O (1), the gold(iii) diethylenetriamine complex {[Au(dien)Cl]@CB[8]}Cl₂·11H₂O (2), and the gold(iii) and platinum(ii) cyclam complexes (H₃O)₅{[Au(cyclam)]@CB[8]}Cl₈·18H₂O (3) and {[Pt(cyclam)]_0.11(H₂cyclam)_0.89@CB[8]}Cl₂·16H₂O (4), respectively, where cyclam is the tetraazamacrocyclic ligand, were synthesized. The inclusion compounds were synthesized both directly starting from CB[8] and the metal complexes with polyamines (en or dien) and by the two-step method with the use of the cyclic polyamine ligand (cyclam) pre-included into the cavity of the macrocycle. The inclusion compounds were characterized by X-ray diffraction (1, 2, and 4), IR spectroscopy, electrospray ionization mass spectrometry, UV-Vis spectroscopy, and thermogravimetric analysis.     

Ten complexes constructed by two reduced Schiff base tetraazamacrocycle ligands: syntheses,structures, magnetic and luminescent properties

Ten new complexes, [Cu₂(L¹)(NO₃)₂]·2H₂O (1), [Cu₄(L¹)₂]·4ClO₄·H₂O (2), [Cu₂(L¹)(H₂O)₂]·(adipate) (3), [Cu₆(L¹)₂(m-bdc)₄]·2DMF·5H₂O (4), [Cu₂(L¹)(Hbtc)]·5H₂O (5), [Cu₂(L¹)(H₂O)₂]·(ntc)·3H₂O (6), [Co₂(L²)]·[Co(MeOH)₄(H₂O)₂] (7), [Co₃(L²)(EtOH)(H₂O)] (8), [Ni₆(L²)₂(H₂O)₄]·H₂O (9) and [Zn₄(L²)(OAc)₂]·0.5H₂O (10), have been synthesized. 1 displays a [Cu₂(L¹)(NO₃)₂] monomolecular structure. 2 shows a supramolecular chain including [Cu₂L¹]²⁺. In 3, two Cu(II) ions are connected by L¹ to form a [Cu₂(L¹)(H₂O)₂]²⁺ cation. In 4, the m-bdc anions bridge Cu(II) ions and L¹ anions to form a layer. Both 5 and 6 display 3-D supramolecular structures. 7 consists of both [Co₂L²]^2? and [Co(MeOH)₄(H₂O)₂]²⁺ units. 8 and 9 show infinite chain structures. In 10, Zn(II) dimers are linked by L² to generate a 3-D framework. The magnetic properties for 4 and 8 and the luminescent property for 10 have been studied.     

Supramolecular Systems Based on Ca2+, [Mo3O2S2Cl6(H2O)3]2s-, [Mo3S4Cl6.75Br0.25(H2O)2]3s- and Cucurbit[6]uril

Adducts of cucurbit[6]uril with Ca²⁺ and trinuclear cluster chloroaquacomplexes (H₉O₄)₂(H₇O₃)₂[(Ca(H₂O)₅)2(C₃₆H₃₆N₂₄O₁₂)]Cl₈·0.67H₂O (1) and [(Ca(H₂O)₅)₂(C₃₆H₃₆N₂₄O₁₂)]× [Mo₃O₂S₂Cl₆(H₂O)₃]₂·13H₂O (2) are obtained and structurally characterized. The structures of both compounds contain polymeric [Ca(H₂O) _n ]₂² CB[6]∞ cations that form infinite columns; the space between them is filled with Cl^s- (1) and [Mo₃O₂S₂Cl₆(H₂O)₃]^2s- (2). A new (H₇O₃)₂(H₅O₂)× [Mo₃S₄Cl_6.25Br_0.25(H₂O)₂](C₃₆H₃₆N₂₄O₁₂)·CH₂Cl₂·6H₂O complex (3) is also obtained and structurally characterized.     

Mixed-ligand platinum(IV) complexes with amino acids and adenine

Complexing in platinum(IV)-adenine-amino acid (α-alanine (Ala), lysine (Lys), or histidine (His)) systems was studied by pH titration. The stability constants of 1: 1: 1 complexes were determined. The stability of these mixed-ligand complexes changes in the following order: Lys < Ala < His. Reactions between aqueous solutions of H₂PtCl₆ and amino acids produced the following coordination compounds: Pt(C₃H₆NO₂)(C₅H₅N₅)Cl₃ · 2H₂O, or Pt(Ala^?)(Ade)Cl₃ · 2H₂O (I); Pt(C₅H₅N₅)(C₆H₁₄N₂O₂)Cl₄ · 2H₂O, or Pt(Ade)(Lys)Cl₄ · 2H₂O (II); and Pt(C₅H₅N₅)(C₆H₉N₃O₂)Cl₄ · 3H₂O or Pt(Ade)(Hist)Cl₄ · 3H₂O (III). These complexes were characterized by ¹³C NMR, IR, and X-ray photoelectron spectroscopy. Alanine is complexed via both amino and carboxy groups; lysine, via α-amino group exclusively; and histidine, via the amino group and the N3 heterocyclic atom. Adenine in these complexes is monodentate due to the N7 heterocyclic atom. The adenine amino group is apparently H-bonded to a water oxygen atom.     

Crystal Structures and Hydrogen Bonding of Two Complexes containing the [Ammine‐chlorido‐ethylenediamine‐bis(pyridine)cobalt(III)]2+ Cation

The crystal structures of two classical cobalt(III) complexes comprising the [CoCl(NH₃)(en)(py)₂]²⁺ cation were determined by single‐crystal X‐ray diffraction. Both complexes, dark red [CoCl(NH₃)(en)(py)₂]Cl₂ · H₂O ( 1 ) and purple [CoCl(NH₃)‐(en)(py)₂][HgCl₄] · 1.125H₂O ( 2 ), crystallize in the triclinic space group P1 . In both compounds, the Co atom exhibits a typical octahedral coordination and the configuration index of the complex is OC‐6‐43. In the case of the chloride ( 1 ), the asymmetric unit comprises one formula unit, whereas there are two formula units in the case of the tetrachloridomercurate ( 2 ). Complex cations, anions, and crystal water molecules are interconnected by various N–H ··· N, N–H ··· Cl, N–H ··· O, O–H ··· Cl, and O–H ··· O bridge bonds. As a result, compound 1 features a two‐dimensional layer structure and compound 2 exists as a three‐dimensional network.     

A Novel Three-Dimensional Network Isophthalato-Bridged Lanthanide Complex: {Ln[C6H4(COO−)2-1,3](CH3COO−)(H2O)2}·H2O

The three-dimensional network of lanthanide (III) complexes with isophthalato (IPT) ligand, (Eu[C₆H₄(COO^?)₂-1,3](CH₃COO^?)(H₂O)₂}·H₂O 1 and {Sm[C₆H₄(COO^?)₂-1,3](CH₃COO^?) (H₂O)₂} H₂O 2, has been prepared by the hydro(solvo)thermal reaction of Eu(C1O₄)₃·6H₂O or Sm(C1O₄)₃·6H₂O, 1,3-dicyanobenzene and acetic acid in the presence of ethanol and H₂O. In the reaction, 1,3-dicyanobenzene was hydrolyzed to give IPT ligand. Single crystal x-ray analysis revealed that crystals 1 and 2 are isomorphous with the isostructural {M[C₆H₄(COO^?)₂-1,3](CH₃COO^?)(H₂O)₂}·H₂O unit. In 1 and 2, IPT acts as a bridging ligand to connect three adjacent metal atoms, forming a network like an undulating sheet paralleling the bc plane. The carboxylate from acetate bridges two adjacent metal atoms in a tridentate mode between the different sheets to extend the structure into a three-dimensional network.     

Self-assembly of copper(II) complexes with substituted aroylhydrazones and monodentate N-heterocycles: synthesis,structure and properties

Two ternary copper(II) complexes [Cu(L¹)(py)] (1) and [Cu(L²)(Himdz]?·?CH₃OH (2) with substituted aroylhydrazones, 5-bromo-salicylaldehyde-3,5-dimethoxy-benzoylhydrazone (H₂L¹) and 5-bromo-salicylaldehyde-p-methyl-benzoylhydrazone (H₂L²), pyridine (py) and imidazole (Himdz), have been synthesized. Their crystal structures and spectroscopic properties have been studied. In each complex, the metal is in a square-planar N₂O₂ coordination formed by the phenolate-O, the imine-N and the deprotonated amide-O atoms of L^2?, and the sp²?N atom of the neutral heterocycle. In the solid state, 1 exists as a centrosymmetric dimer due to very weak apical coordination of the metal bound phenolate-O. Complex 2 has no such apical coordination and exists as a monomer. Self-assembly via C–H?···?O, N–H?···?O and O–H?···?N interaction leads to a one-dimensional chain arrangement; other non-covalent interactions such as C–H?···?π and π?···?π are not involved.     

2,7-萘二磺酸阴离子导向五元瓜环基超分子自组装体的制备及其荧光检测性能

通过引入2,7-萘二磺酸(2,7-NDA^2-)阴离子作为结构导向剂,与五元瓜环(Q[5])和过渡金属离子(Co²⁺、Ni²⁺、Zn²⁺、Cd²⁺)在水热条件下制备了4种新颖的Q[5]基超分子自组装体(Q[5]-SA),即{[M (H₂O)₄(Q[5])]·(NDA)}·xH₂O (M=Co (1)、Ni (2)、Zn (3))和{[Cd₂Cl₂(H₂O)₄(Q[5])]·(NDA)}·13H₂O (4)。单晶X射线衍射测试结果表明,自组装体1~3同构,其中Q[5]仅一端的部分端口羰基氧原子与金属离子配位形成简单配合物;而4中Q[5]的2个端口均与金属离子Cd²⁺配位形成了一维配位链。在自组装体1~4中,配体2,7-H₂NDA均全脱质子,形成2,7-NDA^2-阴离子平衡体系电荷,但均未能与金属离子配位,而在2,7-NDA^2-阴离子与Q[5]外壁之间的瓜环外壁作用下进一步形成三维超分子结构。此外,还研究了自组装体1和4的荧光传感性能,结果表明它们都能够作为抗生素诺氟沙星(NFX)的比率型荧光探针。     

Crystal structures of complexes of 3,5,6-tris(2-pyridyl)-1,2,4-triazine: [Pb(TPT)(NO3)2] n and [Pb(TPT)2(ClO4)(H2O)] · ClO4 · H2O

Two new Pb(II) complexes, [Pb(TPT)(NO₃)₂] _n (1) and [Pb(TPT)₂(ClO₄)(H₂O)] · ClO₄ · H₂O (2) (TPT is the abbreviation of 3,5,6-tris(2-pyridyl)-1,2,4-triazine), have been synthesized and characterized by single-crystal X-ray diffraction. Lead(II) in the compounds of 1 and 2 is nine coordinate (rare mode), PbN₃O₆ and PbN₆O₃, respectively. Both have hemidirected coordination geometries. The supramolecular features in these complexes are guided/controlled by hydrogen bonding and weak directional intermolecular C–H ··· O and π ··· π interactions. The thermal stabilities of 1 and 2 were investigated by thermogravimetric measurements.     

Syntheses and crystal structures of copper(II) complexes derived from 2,4,6-tris(2-pyridyl)-1,3,5-triazine

Treatment of freshly precipitated Cu(OH)₂?·?xH₂O and 2,4,6-tris(2-pyridyl)-1,3,5-triazine (tptz) with oxalic and malonic acids in methanol-water at room temperature gave [Cu(tptz)(C₂O₄)(H₂O)]?·?4H₂O (1) and [Cu(pma)(C₃H₂O₄)(H₂O)]?·?H₂O (2) (pma?=?2-aminocarbonylpyridine), respectively. Reaction in the absence of any acid resulted in [Cu(bpca)(tca)]?·?2H₂O (3) (bpca?=?bis(2-pyridylcarbonyl)amide anion; tca?=?2-pyridinecarboxylate anion). Complex 1 consists of [Cu(tptz)(C₂O₄)(H₂O)] and lattice H₂O molecules; the tridentate tptz ligand, bidentate oxalate dianion and an aqua ligand are bound to Cu with distorted octahedral geometry. Complex 2 is composed of [Cu(pma)(C₃H₂O₄)(H₂O)] and lattice H₂O molecules; the bidentate 2-aminocarbonylpyridine ligand, a bidentate malonate dianion and an aqua ligand are coordinated to Cu with a slightly distorted square pyramidal geometry. Complex 3 consists of [Cu(bpca)(tca)] and lattice H₂O molecules. Square pyramidally coordinated Cu atoms are surrounded by tridentate bpca with nitrogen donor atoms and a bidentate 2-pyridinecarboxylate anion.     

Two solvent directed zinc(II) coordination polymers with 1-D single-zigzag chain and 1-D double-zigzag chains

Two coordination polymers, {[Zn(NiL)(DMA)(H₂O)₂] (DMA)(H₂O)} _n (1) (DMA?=?N,N-dimethylacetamide) and {[Zn₂(NiL)₂(DMF)(H₂O)₄]?·?3DMF} _n (2) (DMF?=?N,N-dimethylformamide), have been prepared by reactions of Zn(NO₃)₂?·?6H₂O and NiL in CH₂Cl₂-DMA–H₂O and CH₂Cl₂-DMF–H₂O, respectively. H₂L denotes dimethyl 5,6,7,8,15,16-hexahydro-6,7-dioxodibenzo-9,10-benzo-[1,4,8,11]tetraazacyclotetradecine-13,18-dicarboxylate. Single-crystal X-ray diffraction analyses reveal that coordination geometries around Ni(II) are identical with slightly distorted square planar and all Ni–N bonds are very short. Complex 1 shows 1-D zigzag chain structure, while 2 has 1-D double-zigzag chains. The chains, which are packed parallel in 1 and 2, are interconnected by lattice solvent through O–H···O and C–H···O hydrogen bonds to form 3-D supramolecular networks. We discuss solvent effects on assembly of the two coordination polymers. The results reveal that coordinated solvent has influence on the assembly procedure.     

Inclusion compounds of the copper(<Emphasis Type="SmallCaps">ii</Emphasis>) and zinc(<Emphasis Type="SmallCaps">ii</Emphasis>) complexes with cyclam in cucurbit[8]uril: synthesis and structure

Inclusion compounds of the macrocyclic cavitand cucurbit[8]uril (CB[8], C₄₈H₄₈N₃₂O₁₆) with the copper(ii) and zinc(ii) complexes with the tetraazamacrocyclic ligand cyclam, {[Cu(cyclam)(H₂O)₂]@CB[8]}Cl₂·18H₂O (1) and {[Zn(cyclam)]@CB[8]}Cl₂·13H₂O (2), were synthesized. The compounds were characterized by X-ray diffraction analysis, electrospray mass spectrometry, IR spectroscopy, and elemental analysis. The ¹H and ¹³C NMR method revealed only one trans-isomer of the zinc(ii) complex with cyclam in an aqueous solution of inclusion compound 2.     

Aqua(2,2′‐bi‐1H‐imidazole)chloro­copper(II) chloro­(imino­diacetato)copper(II) monohydrate

In the title compound, [CuCl(C₆H₆N₄)(H₂O)][Cu(C₄H₅NO₄)Cl]·H₂O, the Cu^II atom in the cation is coordinated by one Cl⁻ ion, two N atoms of the 2,2′‐biimidazole ligand and one aqua ligand. Within the anion, the Cu^II atom is bonded to one Cl⁻ ion, and one N and two O atoms of the imino­diacetate ligand. Neighbouring cations and anions are connected to each other by Cu·Cl semi‐coordination bonds of 2.830 (12) and 3.071 (12) Å, forming a Cu₂Cl₂ rectangular unit. The dinuclear units further link into a polymeric chain along the a axis through Cu·O_aqua interactions of 2.725 (3) Å. Including the long coordination bonds, the geometries around the Cu atoms in the cation and anion are square‐pyramidal and distorted octahedral, respectively.     

抗衡阴离子PF6-调控的1,3-丙二胺缩邻香兰素镧(Ⅲ)配合物的合成和晶体结构

通过柔性配体1,3-丙二胺缩邻香兰素(H2L)与和La(NO3)3.6H2O反应,合成了1个由2个H2L桥连的双核稀土配合物[La2(NO3)6(H2L)2].CH2Cl2(1),该配合物与(NH4)(PF6)继续反应生成了1个由2个NO3-离子桥连的双核配合物[La2(NO3)2(H2L)4](PF6)4.4H2O.2CH2Cl2(2),X-射线单晶衍射分析确定了2个配合物的晶体结构。配合物1和2为结构完全不同的2个双核结构,因抗衡阴离子PF6-有去阴离子的作用,配合物1中的NO3-离子被配体取代,导致配合物1的结构翻转,形成了1个新颖的双核结构2。     

Zinc(ΙΙ) complexes with 5,6-dihydro-1,4-dithiin-2,3-dicarboxylic anhydrate and different N-donors: syntheses,crystal structures,and emission properties

Two new Zn^II complexes, {[Zn(L)(phen)(H₂O)]?·?H₂O}_∞ (1) and {[Zn(L)(4bpy)(H₂O)]?·?H₂O}_∞ (2) (L?=?5,6-dihydro-1,4-dithiin-2,3-dicarboxylate, phen?=?1,10-phenanthroline, and 4bpy?=?4,4′-bipyridine), have been prepared by in situ reaction of Zn(ClO₄)₂?·?6H₂O with 5,6-dihydro-1,4-dithiin-2,3-dicarboxylic anhydrate in the presence of lithium hydroxide, together with incorporating chelating phen or bridging 4bpy as co-ligands. Their structures were determined by single-crystal X-ray diffraction. Complex 1 takes a 1-D helical structure that is further assembled into a 2-D network by O–H?···?O, C–H?···?O hydrogen bonds, and weak S?···?S interactions, and then an overall 3-D supramolecular framework was formed by π?···?π stacking interactions. Complex 2 possesses a 2-D (4,4)-layered structure. The structural difference between 1 and 2 can be attributed to the different N-donor auxiliary co-ligands. Both 1 and 2 are photoluminescent materials whose emission properties are closely related to their intrinsic structure.     

Novel platinum(II) and (IV) complexes of naphthaldimine schiff bases

Naphthaldimines containing N₂O₂ donor centers react with platinum(II) and (IV) chlorides to give two types of complexes depending on the valence of the platinum ion. For [Pt(II)], the ligand is neutral, [(H₂L¹)PtCl₂]·3H₂O (1) and [(H₂L³)₂Pt₂Cl₄]·5H₂O (3), or monobasic [(HL²)₂Pt₂Cl₂]·2H₂O (2) and [(HL⁴)₂Pt]·2H₂O (4). These complexes are all diamagnetic having square-planar geometry. For [Pt(IV)], the ligand is dibasic, [(L¹)Pt₂Cl₄(OH)₂]·2H₂O (5), [(L²)Pt₃Cl₁₀]·3H₂O (6), [(L³)Pt₂Cl₄(OH)₂]·C₂H₅OH (7) and [(L⁴)Pt₂Cl₆]·H₂O (8). The Pt(IV) complexes are diamagnetic and exhibit octahedral configuration around the platinum ion. The complexes were characterized by elemental analysis, UV-Vis and IR spectra, electrical conductivity and thermal analyses (DTA and TGA). The molar conductances in DMF solutions indicate that the complexes are non-ionic. The complexes were tested for their catalytic activities towards cathodic reduction of oxygen.