柔性配体构筑的三个构象多样的镧系羧酸配位聚合物:合成,结构和荧光性质

利用2,2''-(1,4-亚苯基)二(亚苯基)二(硫基)苯二羧酸(H₂L¹)和2,2''-(2,3,5,6-四甲基-1,4-亚苯基)二(亚甲基)二(硫基)苯二甲酸(H₂L²)2个柔性二羧酸分别与镧系金属盐反应,通过溶剂热方法合成了3个配位聚合物:{[(NH₂(CH₃)₂][Nd(L¹)₂(DMF)]·2DMF}_n(1)和{[Ln(L²)_1.5(H₂O)(DMF)₂]·2DMF}_n[Ln=Ce(2),Pr(3)]。利用元素分析、红外、粉末X射线衍射、热重分析等对配合物进行了表征。X射线单晶衍射分析表明:3个配合物均为二维的层状结构,并且2个配体在配合物中表现出不同的构象。(L¹)^2-在配合物1中表现出顺式和反式2种构象,(L2²)^2-在配合物2和3中仅表现出反式构象。此外,对配合物的热稳定性和荧光性质也进行了研究。     

三个二羧酸配体配位聚合物的合成、结构表征和荧光性质

以羧酸配体 2,2''-(1,4-亚苯基双(亚苯基))双(硫二基)二苯甲酸(H₂L¹)和 2,2''-(2,3,5,6-四甲基-1,4-亚苯基)双(亚甲基）双(硫二基)二苯甲酸(H₂L²)分别与金属盐反应,通过溶剂热方法合成了 3个配位聚合物：{[Ni(L¹)(H₂O)₄]·2H₂O}_n (1)、[Zn(L¹)(DMA)₂]_n(2)和[Co(L²)(DMF)₂]_n (3),其中DMA=N,N-二甲基乙酰胺,DMF=N,N-二甲基甲酰胺。对配合物1~3进行了单晶X射线衍射、元素分析、红外光谱、热重分析、粉末X射线衍射和固体紫外可见光谱测试和表征。单晶X射线衍射表明：3个配合物均为一维锯齿形链状结构,并通过氢键作用形成三维骨架,且配体均表现为反式构象。此外,对配合物2固态荧光性质进行了研究。     

柔性配体构筑的三个构象多样的镧系羧酸配位聚合物:合成,结构和荧光性质

利用2,2''-（1,4-亚苯基）二（亚苯基）二（硫基）苯二羧酸（H₂L¹）和2,2''-（2,3,5,6-四甲基-1,4-亚苯基）二（亚甲基）二（硫基）苯二甲酸（H₂L²）2个柔性二羧酸分别与镧系金属盐反应,通过溶剂热方法合成了3个配位聚合物：{[（NH₂（CH₃）₂][Nd（L¹）₂（DMF）]·2DMF}_n（1）和{[Ln（L²）_1.5（H₂O）（DMF）₂]·2DMF}_n[Ln=Ce（2）,Pr（3）]。利用元素分析、红外、粉末X射线衍射、热重分析等对配合物进行了表征。X射线单晶衍射分析表明：3个配合物均为二维的层状结构,并且2个配体在配合物中表现出不同的构象。（L¹）^2-在配合物1中表现出顺式和反式2种构象,（L²）^2-在配合物2和3中仅表现出反式构象。此外,对配合物的热稳定性和荧光性质也进行了研究。     

三个二羧酸配体配位聚合物的合成、结构表征和荧光性质

以羧酸配体2,2''-（1,4-亚苯基双（亚甲基））双（硫二基）二苯甲酸（H₂L¹）和2,2''-（2,3,5,6-四甲基-1,4-亚苯基）双（亚甲基）双（硫二基）二苯甲酸（H₂L²）分别与金属盐反应,通过溶剂热方法合成了3个配位聚合物：{[Ni（L¹）（H₂O）₄]·2H₂O}_n （1）、[Zn（L¹）（DMA）₂]_n （2）和[Co（L²）（DMF）₂]_n （3）,其中DMA=N,N-二甲基乙酰胺,DMF=N,N-二甲基甲酰胺。对配合物1~3进行了单晶X射线衍射、元素分析、红外光谱、热重分析、粉末X射线衍射和固体紫外可见光谱测试和表征。单晶X射线衍射表明：3个配合物均为一维锯齿形链状结构,并通过氢键作用形成三维骨架,且配体均表现为反式构象。此外,对配合物2固态荧光性质进行了研究。     

Syntheses,structures, and luminescence of coordination compounds based on N-containing polycarboxylates

Six coordination compounds constructed by two structurally related flexible nitrogen-containing polycarboxylate ligands 2,2′-(2,2′-(ethane-1,2-diylbis(oxy))bis(2,1-phenylene))bis(methylene)bis(azanediyl)dibenzoic acid (H₂L1) and 5,5′-(2,2′-(ethane-1,2-diylbis(oxy))bis(2,1-phenylene))bis(methylene)bis(azanediyl)diisophthalic acid (H₄L2) have been synthesized: [Ni(H₂O)₆]?·?L1?·?(C₂H₅OH)_0.5?·?H₂O (1), [Co(L1)(L3)]?·?CH₃OH (2), [Ni(L1)(L3)]?·?CH₃OH (3), [Zn(L1)(L3)]?·?CH₃OH (4), [Cd(L1)(L3)]?·?CH₃OH (5), and [Zn(L2)_0.5(phen)]?·?C₂H₅OH (6), where L3?=?3,4?:?9,10?:?17,18?:?23,24-tetrabenzo-1,12,15,26-tetraaza-5,8,19,22-tetraoxacyclooctacosan and phen?=?1,10-phenanthroline. The crystal structures have been determined by single-crystal X-ray diffraction. Compound 1 displays a discrete structure, which is further linked by hydrogen bonds to form a 2-D supramolecular layer. Compounds 2–5 display similar structures. These compounds possess 1-D meso-chain structures linked by L1 and metals. The C–H?···?π interactions from neighboring chains extend the chains in different directions, giving a 3-D plywood network. Compound 6 possesses 2-D layers, which are further linked by hydrogen-bonding interactions to generate a 3-D supramolecular architecture.     

Structural diversity of homochiral cadmium-camphorates with 2,2′-bipyridine

Homochiral framework materials are of current interest due to their potential applications in asymmetric catalysis and enantioselective separation. Four new Cd(II) camphorates (1–4) with 2,2′-bipyridine ligand (= 2,2′-bipy) are successfully synthesized and show distinct structural features. Such rich Cd-cam-2,2′-bipy system is composed of four compounds, [Cd(d-cam)(2,2′-bipy)(DMF)]_n (1), [Cd(d-cam)(2,2′-bipy)(H₂O)]_n (2), [Cd₂(d-cam)₂(2,2′-bipy)₂]_n (3) and [Cd₂Cu₂(d-cam)₄(2,2′-bipy)₂]_n·4nH₂O (4), which are obtained under different conditions. Both compounds 1 and 2 show infinite homochiral Cd-camphorate chain, while compounds 3 and 4 exhibit homochiral layered structures based on different dinuclear units. The results demonstrate the rich coordination chemistry of the enantiopure d-camphorate ligand and the structural diversity of metal-camphorate compounds.     

A one‐dimensional cadmium metal–organic chain based on a [Cd4(COO)4] secondary building unit and a flexible dicarboxylic acid ligand

An infinite one‐dimensional cadmium metal–organic chain, namely catena‐poly[aquabis(μ₃‐2,2′‐{[1,2‐phenylenebis(methylene)]bis(sulfanediyl)}dibenzoato)dicadmium(II)], [Cd₂(C₂₂H₁₆O₄S₂)₂(H₂O)]_n, was synthesized by solvothermal reaction of Cd(NO₃)₂·4H₂O and 2,2′‐{[1,2‐phenylenebis(methylene)]bis(sulfanediyl)}dibenzoic acid (H₂L). The Cd^II centres have six‐coordinate CdS₂O₄ and CdSO₅ geometries. Due to the flexible –CH₂–S– arms, the L²⁻ ligand adopts both syn and anti conformations. Four Cd^II cations are linked by two syn L²⁻ ligands to form a centrosymmetric planar tetranuclear Cd^II core, which is further extended through bonding to the anti L²⁻ ligands to form a one‐dimensional metal–organic chain. Adjacent one‐dimensional chains are connected by C—H...π interactions and nonclassical C—H...O hydrogen bonds to form the resultant three‐dimensional supramolecular framework.     

Microwave-assisted synthesis of novel bis(2-thioxothiazolidin-4-one) derivatives as potential GSK-3 inhibitors

(5Z,5′Z)-3,3′-(1,4-Phenylenebis(methylene)-bis-(5-arylidene-2-thioxothiazolidin-4-one) derivatives (5a-r) have been synthesized by the condensation reaction of 3,3′-(1,4- or 1,3-phenylenebis(methylene))bis(2-thioxothiazolidin-4-ones) (3a,b) with suitably substituted aldehydes (4a-f) or 2-(1H-indol-3-yl)2-oxoacetaldehydes (8a-c) under microwave conditions. The bis(2-thioxothiazolidin-4-ones) were prepared from the corresponding primary alkyl amines (1a,b) and di-(carboxymethyl)-trithiocarbonyl (2). The 2-(1H-indol-3-yl)-2-oxoacetaldehydes (8a-c) were synthesized from the corresponding acid chlorides (7a-c) using HSnBu₃.     

Design and synthesis of two-dimensional pillared MOF layers by connecting infinite one-dimensional chains via 4,4′-bipyridine

Two novel metal-organic frameworks, [Cd(Bna)(DMF)₂(H₂O)₂] _n · nDMF (I) (Bna = 2,2′-dihydroxy-l,l′-dinaphthyl-3,3′-dicarboxylate) and [Cd(Bna)(Bipy)(DMF)₂] _n (II) (Bipy = 4,4′-bipyridine) have been synthesized under mild conditions and structurally characterized. Crystal structural analyses reveal that complex I adots a 1D spiral structure with DMF guest molecules in the spiral by hydrogen bondings. Complex II is constructed by -Cd-Bna-Cd- zigzag chains, which are further connected by Bipy into a 2D sheet. X-ray powder diffraction and thermogravimetric analyses for I and II show that they are highly themally stable in the solid state.     

Hydrothermal synthesis and structure characterization of two six-connected metal–organic frameworks based on the mixed ligands

Two metal–organic frameworks, namely, [Ni₂(BIMB)₂(ndd)₂·H₂O]_n (1) and [Zn₃(ndd)_2.5(μ₃-OH)(1,3-dpp)]_n (2) (H₂ndd = 2,2′-(naphthalene-1,5-diylbis(oxy))diacetic acid, BIMB = 1,4-bis[(1H-imidazol-1-ly)methyl]benzene, 1,3-dpp = 1,3-di(pyridin-4-yl)propane) have been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction and thermogravimetric analysis. Compound 1 presents a two-dimensional network with point symbol of (3⁶·4⁶·5³)-hxl topology. Moreover, compound 2 displays a novel 2-fold interpenetrated structure with the point symbol of (4¹²·6³)-pcu topology based on the hexanuclear [Zn₆(CO₂)₁₀(N)₄] unit as a six-connected node. Meanwhile, compound 2 shows good fluorescence property in the solid state at room temperature.     

A combination of experiment and molecular simulation studies on a new metal-organic framework showing pH-triggered drug release

A new Co(II)-based complex { [Co₂(L)(4,4'-Bipy)₂] · CH₃CN} _n (I) (H4L = 5,5'-(biphenyl-4,4'- diyl-bis(methylene))bis(oxy)diisophthalic acid, 4,4'-Bipy = 4,4'-bipyridine) has been synthesized and structurally characterized. Single-crystal X-ray analysis (CIF file CCDC no. 1406388) reveals that compound I has 3D pcu topology. The incorporation of the drug 5-fluorouracil (5-FU) into the desolvated I was around 15.0 wt % of dehydrated I. Complex I also shows a pH-triggered controlled drug release property. In addition, we used semiempirical AM1 method to investigate the adsorption of 5-FU to I at the molecular level.     

Enantioselective addition of diethylzinc to aromatic aldehydes catalyzed by Ti(IV) complexes of C2-symmetrical chiral BINOL derivatives

Enantioselective addition of diethylzinc to a series of aromatic aldehydes is developed using new chiral C₂-symmetric ligand (S)-2,2′-(1,1′-binaphthyl-2,2′-diylbis(oxy))bis(methylene)bis(4-nitrophenol) (S)-2b. The catalytic system employing 10 mol % of (S)-2b and 120 mol % of Ti(OiPr)₄ was found to promote the addition of diethylzinc to a wide range of aromatic aldehydes with electron-donating and electron-withdrawing substituents, giving up to 89% ee and up to 95% yield of the corresponding secondary alcohol under mild conditions.     

Titanium complexes with sulfur‐linked bis(phenolate) ligands

High‐quality crystals of two bis(phenolate)titanium complexes, namely dichlorido{4,4′‐dimethyl‐2,2′‐[cyclohexane‐1,2‐diylbis(sulfanediyl)]diphenolato}titanium(IV), [Ti(C₂₀H₂₂O₂S₂)Cl₂], (I), and dichlorido{2,2′‐[cyclohexane‐1,2‐diylbis(sulfanediyl)]diphenolato}titanium(IV), [Ti(C₁₈H₁₈O₂S₂)Cl₂], (II), were obtained by reactive crystallization. Depending on the solvent, compound (II) was obtained as unsolvated (IIa) or as the toluene hemisolvate, [Ti(C₁₈H₁₈O₂S₂)Cl₂]·0.5C₇H₈, (IIb). These systems without bulky substituents on the aromatic phenolate rings serve as ideal model compounds for precatalysts. The excellent X‐ray diffraction data will help clarify the nature of the mismatched interactions between the soft S atoms within the ligand and the hard titanium center. Molecule (I) has crystallographic C₂ symmetry.     

A tetradentate bisoxime and its supramolecular nickel(II) cluster: synthesis,crystal structure,and spectral properties

Salen-type bisoxime 5,5′-dimethoxy-2,2′-[(ethylenedioxy)bis(nitrilomethylidyne)]diphenol (H₂L) and its trinuclear Ni(II) cluster {[(NiL)(n-BuOH)]₂(μ-OAc)₂Ni}?·?n-BuOH have been synthesized and structurally characterized. The structure of H₂L adopts an L-shape conformation where the two salicylaldoxime moieties are well separated. In the trinuclear Ni(II) cluster, two acetates coordinate to three Ni(II)'s through Ni–O–C–O–Ni bridges, four μ-phenoxos from two [NiL(n-BuOH)] units also coordinate to Ni(II), and two n-butanols coordinate to two terminal Ni(II)'s forming a distorted octahedral geometry. The Ni–O–C–O–Ni and μ-phenoxo bridges play important roles in assembling Ni(II) and the ligands. H₂L forms a rectangle-like large cave structure through O–H?···?N, C–H?···?O, and C–H?···?π hydrogen-bond interactions, whereas its trinuclear Ni(II) cluster exhibits a 3-D supramolecular network structure through intermolecular O–H?···?O, C–H?···?O, and C–H?···?π hydrogen-bond interactions.     

Enhancing single-molecule magnet behavior of linear Co<Superscript>II</Superscript>-Dy<Superscript>III</Superscript>Co<Superscript>II</Superscript> complex by introducing bulky diamagnetic moiety

Single-molecule magnets (SMMs) are regarded as promising candidates for ultrahigh-density storage, quantum information processing and molecular spintronics. It is a crucial challenge for chemists to modulate magnetic dynamics of SMMs. Here, we successfully synthesized two 3d-4f polynuclear compounds [Co₂Dy(TTTT^Cl)₂(MeOH)]NO₃·3MeOH (1) and [Co₂Dy(TTTT^Cl)₂ (MeOH)][Co(HTTTT^Cl)](NO₃)₂·2.5MeOH·2H₂O (2), where H₃TTTT^Cl=2,2′,2′′-(((nitrilotris(ethane-2,1-diyl)) tris(azanediyl)) tris(methylene))tris-(4-chlorophenol). On applying the approach by co-crystallization of bulky diamagnetic moiety, the effective energy barrier enhances from 401 K (1) to 536 K (2), which are both among the highest d-f heterometallic SMMs.     

Synthesis and Properties of a Novel 3D Europium Coordination Polymer with Helical Chain and (3,6)‐Connected rtl Net

The first coordination polymer of 2,2′‐((4‐carboxymethyl‐1,3‐phenylene)bis(oxy)) diacetic acid (H₃L) with europium(III) ion, [Eu(L)(H₂O)]·3H₂O ( 1 ), has been hydrothermally synthesized and structurally characterized. Complex 1 exhibits a 3D coordination polymer with helical chain and rtl topology of the point symbol (4·6²)₂(4²·6¹⁰·8³) based on [Eu₂(COO)₄] as secondary building unit (SBU). Furthermore, the luminescent and magnetic properties of complex 1 are studied.     

Structural diversity of transition-metal coordination polymers derived from isophthalic acid and bent bis(imidazole) ligands

Four coordination polymers associated with bent bis(imidazole) 1,3-bis(imidazol-l-yl-methyl)benzene (mbix) and isophthalic acid (H₂ip) or 5-methylisophthalic acid (H₂mip) ligands, formulated as {[Cd(mbix)(mip)]·H₂O} _n (1), {[Co(mbix)(mip)]·0.4H₂O} _n (2) [Ni(mbix)(mip)H₂O] _n (3) and [Ni(mbix)(ip)] _n (4), were synthesized under hydrothermal conditions and characterized by physico-chemical and spectroscopic methods. Complexes 1 and 2 are isomorphous and exhibit a 1D loop-like chain. Complex 3 features a 2D (4,4) layer, which further extends into an unusual 2D (3,5)-connected 3,5L2 double-layered supramolecular network via classical O–H···O hydrogen bonding interactions. Complex 4 is a 3D network, which shows a rare binodal (3,5)-connected 3,5T1 framework. Moreover, the luminescence and catalytic properties of the complexes for the degradation of methyl orange by sodium persulfate in a Fenton-like process are reported.     

Synthesis,structure and characterization of new 1D and 2D Ni(II) coordination polymers

Two new Ni(II) coordination polymers, namely [Ni₃(Hsdac)₂(sdac)₂(2,2′-bipy)₂] (1) and [Ni₂(sdac)₂(4,4′-bipy)₂]·2H₂O (2) (sdba = 4,4′-sulfonyldibenzoate, 2,2′-bipy = 2,2′-bipyridine, 4,4′-bipy = 4,4′-bipyridine), have been prepared under hydrothermal conditions and characterized by single crystal X-ray diffraction analyses. Compound 1 possesses an interesting chain structure. Adjacent chains are further linked through H-bond interactions between Hsdac ligands to give a two-dimensional (2D) supramolecular architecture. Compound 2 displays an unusual 2D polyrotaxane-like network.     

含吡啶二脲配体汞(II)、镉(II)配合物的合成及其晶体结构

以2,2′-二氨基二苯醚和4-吡啶异氰酸酯反应合成了含吡啶二脲配体(L),并分别与HgCl_2和Cd(ClO_4)2进行了配位反应,得到2个配位聚合物{[Hg(L)Cl_2]·2DMF}_n(1)和{[Cd(L)_2(H_2O)_2](ClO_4)_2·4DMF·2H_2O·2CH_3OH}_n(2),采用1H NMR、MS、FTIR和元素分析等对化合物L进行了表征。通过X射线单晶衍射技术测定了配体及2个配合物的单晶结构,结构解析表明,2个配合物均为一维链状结构。进一步考察了2个配合物的热稳定性及其对甲醇蒸气的吸附性能。     

Two new supramolecular compounds based on Ni(II)-Schiff-base and Keggin-type [PMo12O40]3−

Two polyoxometalate-templated nickel-Schiff-base compounds, {[Ni(L)₂]₂[PMo₁₂O₄₀][Cl] · 1.5DMF · H₂O} _n (1) and {[Ni(L)₂]₂[PMo₁₂O₄₀][Cl] · DMSO · CH₃OH · 0.5H₂O} _n (2) (where L is 1,4-bis(4-imidazolyl)-2,3-diaza-1,3-butadiene), were synthesized in situ from Ni²⁺ and L in H₂O/DMF/CH₃OH or H₂O/DMSO/CH₃OH at room temperature and characterized by elemental analysis, infrared spectroscopy, and single-crystal X-ray diffraction analysis. The results of the single-crystal X-ray diffractions suggested that both compounds have the same packing of the Ni(II)-Schiff-base cation layer and Keggin anion layer. Thermogravimetric analyses suggested that two supramolecular compounds have similar thermal stabilities based on the same packing of the cation and anion layers.