2D Wave-like Layer Research Articles

Two Chiral Metal Complex Templated Aluminoborates Constructed from Three Types of Oxoboron Clusters.

The two acentric aluminoborates (ABOs) [M(dap)3]2{Al[B5O7(OH)3][B5O8(OH)2][B6O9(OH)2]} (M and dap represent Co(1)/Ni(2) and 1,2-diaminopropane, respectively) templated by chiral metal complexes (CMCs) have been solvothermally synthesized. The isostructural 1 and 2 crystallize in the chiral space group P21. Both feature unprecedented 2D wavelike layers built by three kinds of oxoboron (B-O) clusters ([B5O7(OH)3]2-, [B5O8(OH)2]3-, and [B6O9(OH)2]2-) and AlO4 tetrahedra. In the frameworks of 1 and 2, AlO4 and [B6O9(OH)2]2- units are strictly alternating into 1D chains. Further, [B5O8(OH)2]3- clusters link adjacent chains to form 2D wavelike layers. In addition, the [B5O7(OH)3]2- units as the hanging clusters are supported on two sides of the wavelike layers through AlO4 groups, resulting in the first example of a wavelike layer ABO composed of three kinds of B-O clusters and four types of channels. 1 and 2 display second-harmonic generation (SHG) signals about ∼1.3 and ∼0.93 times that of KH2PO4 (KDP) and belong to the class of wide-band-gap semiconductors.

Assembly of co coordination polymers tuned by the N-donor ligands with different spacer: Syntheses, structures and photocatalytic properties

Two new CoII-based coordination polymers tuned by the flexible ‘‘V’’-shaped 3,3ˊ-(1,2-phenylenebis(methyleneoxy)) dibenzoic acid (H2L) and different N-donor spacers, namely, [Co(L)(bib)]n (1) and [Co2(L)2(phen)2(H2O)2·H2O]n (2) (bib = 1,4-bis(1-imidazoly)benzene and phen = 1,10-phenanthroline) have been prepared. In 1, the CoII centers are linked by L to form a Co–L chain, which is further extended into a 2D wave-like layer by bib linkers. In 2, the L linker connected the adjacent Co(II) centers into 1D chain, which is joined into a 3D supramolecular structure through H-bonded and π–π stacking interactions. The diverse networks of 1–2 demonstrate that the steric hindrance effect may show significant effect on the final structures. In addition, the title complexes exhibit photocatalytic activity for dye methyl violet (MV) degradation under UV light.

Design of a pillar-layered metal-organic framework as high-performance fluorescence sensor for nitroaromatic compounds

A ternary luminescent cadmium-triazolate-carboxylate framework, [(CH3)2NH2][Cd(1245-BTC)0.5(3S-TRZ)] (SNNU-111, 1245-BTC ​= ​1245-benzenetetra- carboxylic acid, 3S-TRZ ​= ​3-mercaptotriazole) was successfully designed in this work. X-ray single crystal diffraction results show that Cd atoms are connected by 3S-TRZ ligands to form 2D wave-like layers, which are further extended by 1245-BTC linkers to generate the 3D pillar-layered architecture of SNNU-111. Solid-state and solution photoluminescence both showed that the emissions of SNNU-111 was ascribed to the intraligand charge transfer in 1245-BTC. Benefited from this process, SNNU-111 MOF can act as excellent fluorescence sensor to quantitatively detect involved nitroaromatics including nitrobenzene (NB), 1,2-dinitrobenzene (1,2-DNB), 1,3-dinitrobenzene (1,3-DNB), 2,4-dinitrotoluene (DNT), 2,4,6-trinitrotoluene (TNT), and 2,4,6-trinitrophenol (PA) through the fluorescence quenching. The corresponding quenching coefficient (Ksv) values are of 1.0 ​× ​104-1.7 ​× ​104 ​M−1, which surpass the performance of many reported sensors. Specially, the Ksv value of 1.2 ​× ​104 ​M−1 for NB is nearly the highest one among all MOF sensors up to now. On the other hand, SNNU-111 sensor also exhibits good sensitivity to nitroaromatics with the detection limits as low as 1.61–5.77 ​ppm. Overall, the definite pillar-layered structure, fast response and high sensitivity make SNNU-111 a promising fluorescent sensor to detect nitroaromatic compounds.

Syntheses, structure and properties of an especially stable Cd metal-organic framework driven by benzotriazole-5-carboxylic acid

A new two-dimensional (2D) stable cadmium-organic framework, [Cd(btca)(2,2′-bpy)]n (1), has been successfully designed and synthesized by means of solvothermal method (where H2btca = benzotriazole-5-carboxylic acid, 2,2′-bpy = 2,2′-bipyridine). Complex 1 has been characterized by combining single-crystal X-ray diffraction analysis, elemental analysis and IR spectroscopy. Single-crystal X-ray diffraction analysis reveals that 1 possesses 2D wave-like layered structure, and these 2D wave-like layers are interlinked each other by π-π stacking interactions to form supramolecular network. Compound 1 is especially stable in air, water, acidic/basic aqueous solutions (pH = 1 ~ 13) and common organic solvents. Furthermore, MOF 1 is stable up to 460 °C. Therefore, Compound 1 possesses excellent chemical and thermal stabilities, which makes it possible for practical applications. In addition, the optical property of the complex 1 was investigated.

A novel three-dimensional copper(I) cyanide coordination polymer constructed from various bridging ligands: synthesis, crystal structure and characterization.

The cyanide ligand can act as a strong σ-donor and an effective π-electron acceptor that exhibits versatile bridging abilities, such as terminal, μ2-C:N, μ3-C:C:N and μ4-C:C:N:N modes. These ligands play a key role in the formation of various copper(I) cyanide systems, including one-dimensional (1D) chains, two-dimensional (2D) layers and three-dimensional (3D) frameworks. According to the literature, numerous coordination polymers based on terminal, μ2-C:N and μ3-C,C,N bridging modes have been documented so far. However, systems based on the μ4-C:C:N:N bridging mode are relatively rare. In this work, a novel cyanide-bridged 3D CuI coordination framework, namely poly[(μ2-2,2'-biimidazole-κ2N3:N3')(μ4-cyanido-κ4C:C:N:N)(μ2-cyanido-κ2C:N)dicopper(I)], [Cu2(CN)2(C6H6N4)]n, (I), was synthesized hydrothermally by reaction of environmentally friendly K3[Fe(CN)6], CuCl2·2H2O and 2,2'-biimidazole (H2biim). It should be noted that cyanide ligands may act as reducing agents to reduce CuII to CuI under hydrothermal conditions. Compound (I) contains diverse types of bridging ligands, such as μ4-C:C:N:N-cyanide, μ2-C:N-cyanide and μ2-biimidazole. Interestingly, the [Cu2] dimers are bridged by rare μ4-C:C:N:N-mode cyanide ligands giving rise to the first example of a 1D dimeric {[Cu2(μ4-C:C:N:N)]n+}n infinite chain. Furthermore, adjacent dimer-based chains are linked by μ2-C:N bridging cyanide ligands, generating a neutral 2D wave-like (4,4) layer structure. Finally, the 2D layers are joined together via bidentate bridging H2biim to create a 3D cuprous cyanide network. This arrangement leads to a systematic variation in dimensionality from 1D chain→2D sheet→3D framework by different types of bridging ligands. Compound (I) was further characterized by thermal analysis, solid-state UV-Vis diffuse-reflectance and photoluminescence studies. The solid-state UV-Vis diffuse-reflectance spectra show that compound (I) is a wide-gap semiconductor with band gaps of 3.18 eV. The photoluminescence study shows a strong blue-green photoluminescence at room temperature, which may be associated with metal-to-ligand charge transfer.

Five new coordination polymers of s- and d-block metals: Structural diversities, magnetic properties and luminescence

In order to explore the metal ions-controlled syntheses of coordination polymers (CPs), the temperature and solvent ratio were fixed in the reaction processes. By selecting a series of s- and d-block metal ions, five new CPs, [ZnL0.5(H2O)2]n (1), [CoL0.5(H2O)2]n (2), [Mn(H2L)(H2O)2]n (3), [Ca(H2L)(H2O)2]n (4) and [Ba(H2L)(H2O)2]n (5), have been synthesized by employing a less-investigated oxalamide N,N′-bis(4-phthalic acid) (H4L) ligand. H4L shows very versatile coordination modes and leads to various frameworks, including isomorphous 2D grid-like layer based on M2O2 cores for 1 and 2, isomorphous 4-connected 3D PtS frameworks based on 1D [M(CO2)2]n chains for 3 and 4, and a 2D wave-like layer based on [BaO3]n chains for 5.2 and 3 reveal the antiferromagnetic and ferromagnetic properties, respectively, while 1, 4 and 5 possesses strong solid state luminescence.

Structures and photocatalytic performance of two d10 metal-based coordination polymers containing mixed building units

The linker 1,4-bis(2-methyl-imidazole-yl)-butane (bib) was used to construct two coordination polymers, specifically [Cd(bib)(ipa)]n (1) and [Zn(bib)(tpa)]n (2), in the presence of isophthalic acid (H2ipa) and terephthalic acid (H2tpa), respectively, under solvothermal conditions. Topological analyses reveal that the crystal of complex 1 consists of a 3D threefold interpenetrating network with Schlafli symbol {65.8}, while complex 2 possesses a 2D wavelike layer structure with Schlafli symbol {66}. The photocatalytic properties of both complexes for the degradation of methyl violet have been explored, revealing that complex 2 is a better photocatalyst than 1. A mechanism for the photocatalytic properties of the complexes is proposed, based on the results of density of states (DOS) and partial DOS calculations.

Bimetallic Uranyl Organic Frameworks Supported by Transition-Metal-Ion-Based Metalloligand Motifs: Synthesis, Structure Diversity, and Luminescence Properties.

A bifunctional ligand, 2,2'-bipyridine-4,4'-dicarboxylic acid (H2bpdc), has been used in the investigation of constructing bimetallic uranyl organic frameworks (UOFs). Seven novel uranyl-transition metal bimetallic coordination polymers, [(UO2)Zn(bpdc)2] n (1), [Cd(UO2)(bpdc)2(H2O)2·2H2O] n (2), [Cu(UO2)(bpdc)(SO4)(H2O)3·2H2O] n (3), [CuCl(UO2)(bpdc)(Hbpdc)(H2O)2·H2O] n (4), [Cu(UO2)(bpdc)2(H2O)] n (5), [Co2(UO2)3(bpdc)6] n (6), and [Co3(UO2)4(bpdc)8(Hbpdc)(H2O)2] n (7), have been successfully constructed through the assembly of various transition-metal salts, uranyl ions, and H2bpdc ligands under hydrothermal conditions. UOFs 1, 5, 6, and 7 adopt three-dimensional (3D) frameworks with different architectures; UOFs 2 and 3 exhibit two-dimensional (2D) wavelike and stairlike layers, respectively, while UOF 4 is a one-dimensional (1D) chain assembly. These UOFs include a wide range of dimensionalities (1D-3D), interpenetrated frameworks, and cation-cation interaction species, suggesting that anion-dependent structure regulation based on the metalloligand [M(bpdc) m] n- motifs, the coordination modes of the metal centers and bpdc2- ligands, along with the reaction temperature, has a remarkable influence on the formation of bimetallic UOFs, which could be a representative system for the structural modulation of UOFs with various dimensionalities and structures. Furthermore, the thermal stability and luminescent properties of compounds 1, 3, and 6 are also investigated.

PH-Directed assembly of four polyoxometalate-based supramolecular hybrids by using tritopic bridging ligand 1, 3, 5-tris-(1-imidazolyl)-benzene: Structures and electrocatalytic properties

Four new inorganic-organic supramolecular compounds, namely, (H2tib)2[GeW12O40] (1), [Mn(Htib)4][HGeW12O40]2·4H2O (2), [Mn(tib)]2(H2O)6[GeW12O40]·4H2O (3) and [Mn(tib)]2(H2O)6[GeW12O40]·2H2O (4) (tib = 1, 3, 5-tris-(1-imidazolyl)-benzene), have been synthesized through the hydrothermal reaction of [GeW12O40]4- anions, MnII cations and tib ligands under different pH conditions. Compounds 1 and 2 were prepared at lower pH (pH ≈ 2.0 for 1 and 3.2 for 2). Compound 1 exhibits a simple monomer structure. In 2, the Mn cation is coordinated with four tib ligands and two [GeW12 O40]4- anions to form a dimer, in which each of [GeW12 O40]4- anion connects with one Mn cation. Compounds 3 and 4 were prepared at higher pH (pH ≈ 4.2 for 3 and 4.9 for 4), and compounds 3 and 4 display a one-dimensional (1D) chain and a (4, 4)-connected 2D wave-like layer, respectively, and in compound 3, each of GeW12 cluster connects two Mn atoms, however, compound 4: each of GeW12 cluster connects four Mn atoms. The isolation of these four compounds is very informative for systematically understanding the effect of the pH on assembly of polyoxometalate-based hybrids. Also, the electrocatalytic properties of 1–4-CPEs towards nitrite have also been investigated.

A series of transition metal-organic frameworks based on a bipyridinium carboxylate ligand: Syntheses, structures and photoluminescent properties

Based on a bipyridinium carboxylate ligand 1-(3,5-dicarboxy)-benzyl-1,2-di(pyridine-4-yl)ethylene chloride (H2L+Cl−), eight transition metal coordination polymers, namely, {[Zn(L)Cl]⋅4H2O}n (1), {[Zn(L)H2O]⋅NO3⋅2H2O}n (2), {[Zn(L) (H2O)]⋅(NO3)0.5⋅(Cl)0.5⋅2H2O}n (3), {[Cd(L)(H2O)(NO3)]⋅2H2O}n (4), {[Cd1.5(L) (Cl)2]⋅2H2O}n (5), {[Cu(L)(H2O)]⋅NO3⋅H2O}n (6), {[Cu(HL)2(H2O)2]·Cl2·6H2O}n (7) and {[Ni(L)(H2O)Cl]⋅4H2O}n (8) have been synthesized and characterized by single-crystal X-ray diffraction analyses. Complexes 1 and 8 display 2D wave-like layer structures with a 3-connected 63 topology. Complexes 2 and 6 demonstrate 3D 2-fold interpenetrating frameworks with uninodal, 3-connected (10,3)-d utp-topology. Another pair of 3D 2-fold interpenetrating frameworks 3 and 4 possess 3-connected, uninodal 103ThSi2 (ths)-topology. Complex 5 shows a 2D layer structure based on the extending of trinuclear Cd(II) subunits. Complex 7 presents 1D double-chain structure, in which the central Cu(II) ions are connected by the partially deprotonated ligand HL. Additionally, powder X-ray diffractions (PXRD) and thermogravimetric analyses of complexes 1–8, as well as the solid-state luminescent properties of d10 metal complexes 1–4 at room temperature have also been discussed.

Synthesis and structures of a series of d10 coordination compounds based on flexible bis(imidazole) ligand and dicarboxylates

ABSTRACTA series of new coordination compounds based on 1,6-bis(2-methyl-imidazole-yl)-hexane (bimh), namely [Zn(bimh)0.5(chda)]n (1), {[Cd(bimh)0.5(bda)]·H2O}n (2), [Cd(bimh)(oba)]n (3), [Zn(bimh)(oba)]n (4), [Cd(bimh)(ipa)]n (5), {[Zn(bimh)0.5(ipa)]·H2O}n (6), (bimh = 1,6-bis(2-methyl-imidazole-1-yl)hexane, H2chda = 1,4-cyclohexanedicarboxylic acid, H2bda = 2,2′-biphenyldicarboxylic acid, H2oba = 4,4′-oxybis(benzoic acid), and H2ipa = isophthalic acid) have been synthesized by solvothermal route and diffusion method and characterized by elemental analysis, IR spectroscopy, single-crystal X-ray diffraction technology. Compound 1 affords a two-dimensional (2D) wave-like framework with dinuclear paddle-wheel units, where the structures are further assembled via aromatic π–π stacking to generate a 3D network. Compound 2 exhibits a 1D ladder chain, which is further linked by hydrogen bonds to form a 2D architecture. Compounds 3 and 4 are isostructural, possessing a 2D layer network based on hydrogen bonds. Compound 5 displays a 2D wave-like layer structure. Compound 6 has a 1D line chain structure, which is packed into a 3D supermolecule network by two types of hydrogen bonds. Furthermore, the thermal stabilities and photoluminescent properties for compounds 1–6 were investigated.

Synthesis, crystal structure and characterization of a lanthanide complex based on 4-(4-oxypyridinium-1-yl) phthalic acid and 1,10-phenanthroline

ABSTRACTA new lanthanide complex [(Ho(L)(phen)NO3(H2O)]·H2O (1) (H2L = 4-(4-Oxypyridinium -1-yl) phthalic acid, phen = 1,10-phenanthroline) has been afforded under hydrothermal conditions, and characterized by elemental analysis, IR spectra, and X-ray diffraction. In the structure of 1, the L ligand connects Ho(III) atoms through one monodentate and one chelate carboxylate as well as one hydroxy group giving rise to a 2D wavelike polymer layer, which is extended by C–H⋅⋅⋅O hydrogen bond and π⋅⋅⋅π stacking interactions to give rise to a 3D supramolecular network. In addition, PXRD patterns and thermal gravimetric analysis (TGA) of sample 1 were investigated.

Anion-dependent construction of a series of fluorescent coordination polymers based on 1D zinc∩4,4′-bis(imidazol-1-yl)-biphenyl substrates

In this work, the rod-like ligand 4,4′-bis(imidazol-1-yl)-biphenyl (bibp) has been utilized as a building block to carry out counterion effects on the structural diversities of coordination polymers. A series of new zinc complexes, [Zn(trans-bibp)Cl2]∞ (1), [Zn(trans-bibp)Br2]∞ (2), {[Zn(cis-bibp)(Ac)2]·(H2O)}∞ (3), [Zn(trans-bibp)SO4]∞ (4), {[Zn2(cis-bibp)2(ipa)2]·(H2O)}∞ (5, H2ipa=isophthalic acid) and {[Zn(trans-bibp)(cis-bibp)]·(ClO4)2(CHCl3)2(CH3OH)}∞ (6) have been successfully synthesized. Complexes 1 and 2 are iso-structural, which show a 1D W-type chain [Zn(trans-bibp)]∞. Complex 3 exhibits a 2D wave-like layer formed by the hydrogen bond among the 1D linear chain [Zn(cis-bibp)]∞. Complex 4 displays a 2D fish-bone lattice, which is generated from connecting the 1D W-type chain [Zn(trans-bibp)]∞ by the μ2-SO42-. Complex 5 presents an interesting 2D–3D 65·8 architecture, including two 1D chains [Zn(ipa)]∞ and [Zn(cis-bibp)]∞. Complex 6 demonstrates a 2D wave-like layer [Zn(trans-bibp)(cis-bibp)]∞. The structural diversities among 1–6 have been carefully discussed, and the role of counterion in the self-assembly of coordination polymer have also been well documented from the coordination affinity and bridging mode. Furthermore, the solid-state fluorescence properties of 1–6 at room temperature have been studied.

Hydrothermal synthesis, structure and property of transition metal(Mn, Zn, Cd or Pb) coordination frameworks using quinoline-8-oxy-acetate acid and dicarboxylic acid as ligands

Five transition metal coordination compounds, [Mn2(8-qoac)2(bdc)(H2O)4](1)(8-qoacH=quinoline-8-oxy-acetate acid, H2bdc=benzene-1,4-dicarboxylic acid), [Zn4(8-qoac)4(bdc)2] n (2), {[Cd2(8-qoac)2(Hip)2(H2O)2]·(H2O)4} n (3)(H2ip=benzene-1,3-dicarboxylic acid), [Pb3(8-qoac)2(bdc)1.5(H2O)Cl] n (4) and [Zn2(8-qoac)(8-ql)(bdc)] n (5)(8-Hql=8-hydroxyquinoline), were synthesized by hydrothermal syntheses of metal salts with benzenedicarboxylic acid and 8-qoacH. Compound 1 possesses a discrete dimer bridged by bdc2− ligand. Compound 2 presents a 2D layer network constructed from bdc2− linkers and 1D infinite ribbons, in which Zn(II) centers are bridged by 8-qoac− with a tetradentate binding mode. Compound 3 displays a 1D zigzag chain, with adjacent chains further connected via extensive O-H…O hydrogen bonds to generate a 3D supramolecular structure. Compound 4 shows a 3D framework containing trinuclear lead secondary building units and bdc2− linkers, in which a new coordination mode of 8-qoac− ligand is observed. In compound 5, Zn(II) ions are simultaneously bridged by 8-qoac−, 8-ql− and bdc2− ligands to form tetranuclear zinc units, which are further interlinked by bdc2− linkers to yield a 2D wave-like layer. Based on intraligand(IL)(π-π*) fluorescent emission, compounds 1–5 possess strong purple fluorescent emissions. In addition, the thermal stabilities of compounds 1–5 were studied.

Rigidity versus Flexibility of Ligands in the Assembly of Entangled Coordination Polymers Based on Bi- and Tetra Carboxylates and N-Donor Ligands

Seven Zn(II) coordination polymers including [Zn(pbda)(p-bimb)]·H2O (1), [Zn(pbda)(bpa)0.5] (2), [Zn(pbda)(bpp)] (3), [Zn(Hpbda)2(bibm)2] (4), [Zn(pbta)0.5(m-bimb)]·H2O (5), [Zn(pbta)0.5(bpp)(H2O)] (6), and [Zn(H2pbta)(bibm)]·H2O (7) (H2pbda = 4,4′-{[1,4-phenylenebis(methylene)]bis(oxy)}dibenzoic acid; p-bimb = 1,4-bis(1H-imidazol-l-yl)methyl)benzene; bpa = 1,2-bis(4-pyridyl)ethane; bpp = 1,3-bis(4-pyridyl)-propane; bibm = 4,4′-di(1H-imidazol-1-yl)-1,1′-biphenyl; m-bimb = 1,3-bis(1H-imidazol-l-yl)methyl)-benzene; H4pbta = 5,5′-phenylenebis(methylene)-1,1′-3,3′-(benzene-tetracarboxylic acid) were prepared under solvothermal conditions and structurally characterized. Compound 1 shows a three-dimensional (3D) channel-like architecture constructed by helical chain subunits. Compound 2 shows a rare 2D + 2D + 2D → 2D network with both polyrotaxane and polycatenane features. 3 holds a 2D layer structure constituted of metal-sharing right- and left-handed helical chains. Compound 4 presents a one-dimensional (1D) chain which is decorated by long side arms around the chain. Compound 5 possesses a 2D wave-like layer formed by [Zn2(m-bimb)]n chains by linear pbta ligands. Compound 6 displays a 3D framework that is stabilized by hydrogen bonding interactions between the coordinated H2O molecules and the neighboring carboxylate oxygen atoms. Compound 7 possesses a 1D + 1D → 2D polycatenation motif. The results demonstrated that the rigidity versus flexibility of the ligands along with the number of carboxyl groups make an impact on the structural diversities of the entangled coordination polymers. Moreover, compounds 3 and 6 as representative examples possessed high catalytic efficiency for the photodecomposition of methyl blue in water using natural sunlight irradiation.

Effect of central metals and N-donor ligands on the architectures of a series of coordination polymers based on a bis(sulfanediyl) thiadiazole diacetate

Five new transition metal coordination polymers, namely, [Co(bbbm)(BSTDA)] (1), [Co(bdmbmb)(BSTDA)(H2O)]·(H2O) (2), [Ni(bbbm)(BSTDA)(H2O)2] (3), [Ni2(3-dpyh)2(BSTDA)2(H2O)] (4) and [Cd(bbbm)1.5(BSTDA)] (5) have been synthesized from an S-/thiadiazole-containing dicarboxylate [H2BSTDA=bis(sulfanediyl) thiadiazole diacetic acid] and different flexible/semi-rigid N-donor ligands [bbbm=1,1-(1,4-butanediyl) bis-1H-benzimidazole, bdmbmb=1,4-bis(5,6-dimethylbenzimidazole-1-yl)benzene and 3-dpyh=N,N′-bis(3-pyridinecarboxamide)-1,6-hexane]. Structural analysis indicates that the title complexes present different structures although using the same S-/thiadiazole-containing dicarboxylate. Complex 1 is a 3D framework constructed from 2D (63) Co-BSTDA layers and 1D Co-bbbm chains. When the flexible bbbm in 1 was replaced by a semi-rigid bdmbmb ligand, a 2D parallelogram (4,4) network 2 derived from 1D Co-BSTDA and Co-bdmbmb single chains has been obtained. Complex 3, with NiII ion as substitute of CoII ion in 1, exhibited a 2D (4,4) network constructed form 1D Ni-BSTDA and Ni-bbbm single chains. When the bbbm in 3 was replaced by a longer and more flexible N-donor ligand 3-dpyh in 4, a 2D wave-like (4,4) layer constructed from [Ni-BSTDA]2 and [Ni-(3-dpyh)]2 double chains with bimetallic nodes was generated. While the CoII ion in 1 was substituted by CdII ion in 5, a 3D framework crossed by 2D (63) wave-like Cd-bbbm layers and 1D zigzag Cd-BSTDA chains was obtained. Structural diversity in complexes 1–5 demonstrates that the coordination characters of metal ions, the spacer length and flexibility of N-donor ligands have great influence on the final structures of the title complexes. In addition, fluorescence properties of complexes 1–5 are also reported in this paper.

A novel luminescent three-dimensional Ag(I) complex with 3-fold interpenetrating (3,8)-connected nets

A novel luminescent Ag(I) coordination polymer, [Ag3(cpterpy)2]n·nNO3 (1) (Hcpterpy=4-(4-carboxyphenyl)-2,2:4′,4-terpyridine), is built-up from Ag(I) ions and terpyridyl-carboxylate ligands with unusual three different coordination modes. The dinuclear [Ag2O2] units with cpterpy- ligands in 1 are linked to form 2D wave-like layers and further connected by [Ag4O6] units into a 3D network, which features 3-fold interpenetrating (3,8)-connected nets with a (41264812)(462)(462) topology. Complex 1 exhibits interesting solid-state photoluminescence and high thermal stability.

Syntheses, structures and magnetic properties of one family of 3d–4f chiral metal-organic frameworks (MOFs) based on D(+)-camphoric acid

The hydrothermal reactions of D (+)-camphoric acid ( D -H 2 Cam) and 1,10-phenanthroline (phen)/2,2′-bipyridine (2,2′-bipy) with the corresponding metal salts gave rise to eleven chiral 3d–4f heterometallic metal-organic frameworks (MOFs). Single-crystal X-ray diffraction measurements reveal that the crystal structures are isostructural, crystallizing in the orthorhombic space group P 2 1 2 1 2 1 and they exhibit unique three-dimensional chiral 6-connected frameworks involving 1D zigzag chains aligned parallel to the a axis and the 2D wave-like lanthanide layers, with the Schläfli symbol (4 9 · 6 6 ). Moreover, we have systematically investigated the magnetic behaviors of partial compounds. • Eleven chiral 3d-4f MOFs have been synthesized and characterized. • They exhibit unique 6-connected frameworks. • The magnetic behaviors have been systematically investigated. Eleven chiral 3d-4f Metal-Organic Frameworks constructed from D (+)-camphoric acid have been synthesized. The crystal structures exhibit unique three-dimensional chiral 6-connected frameworks. The magnetic behaviors have been systematically investigated.

Synthesis, Structure and Thermal Properties of Two New Nickel(II) Coordination Polymers Based on Diphenic Acid and Bis(Imidazole) Ligands

Two novel nickel(II) coordination polymers, Ni(DPA)(BIX) (1) and Ni2(DPA)2(FBIX)2·H2O (2) (H2DPA = diphenic acid, BIX = 1,4-bis(imidazol-1-ylmethyl)benzene and FBIX = 2,3,5,6-tetrafluoro-1,4-bis(imidazol-1-ylmethyl)benzene), have been synthesized under the hydrothermal conditions and characterized by IR, elemental analysis and single crystal X-ray diffraction. Complex 1 crystallizes in the monoclinic space group C2/c with unit cell dimensions a = 35.504(4) A, b = 7.6014(9) A, c = 19.894(2) A, β = 121.607(2)°, V = 4,572.6(9) A3, Z = 8, R 1 = 0.0461 and wR 2 = 0.1193. Complex 2 crystallizes in the monoclinic space group C2/c with unit cell dimensions a = 21.623(2) A, b = 13.9245(15) A, c = 19.743(3) A, β = 119.2360(10)°, V = 5,187.2(12) A3, Z = 4, R 1 = 0.0399 and wR 2 = 0.1034. Complex 1 affords a two-dimensional (2D) wave-like layer network based on the intersection of Ni-BIX and Ni-DPA chains, while complex 2 is an interesting three-dimensional (3D) 4-connected network with a point symbol of (65.8). A careful structural comparison reveals the similarity of the Ni(II) coordination geometry and ligand binding mode. The significant discrepancy of their network structures may be attributed to the fluorinated substituent group. Two novel nickel(II) coordination polymers have been synthesized under the hydrothermal conditions. Complex 1 affords a two-dimensional (2D) wave-like layer network based on the intersection of Ni-BIX and Ni-DPA chains, while complex 2 is an interesting three-dimensional (3D) 4-connected network with (65.8) topology. The results show that the substituent group plays a significant role in the assembly process.

Characterization and Synthesis of Two New ZnII and CdII-Coordination Polymers Based on 3,3′-Biphenyl Dicarboxylate and N,N’-Donor Co-ligands

Two new 1D coordination polymers, [Zn(3,3′-bpdc)(2,2′-bpy)]n (1) and [Cd (3,3′-bpdc)(2,2′-bpy)]n (2) [3,3′-H2bpdc = 3,3′-biphenyl dicarboxylic acid, 2,2′-bpy = 2,2′-bi pyridine], were rationally designed and synthesized with an identical strategy that employed 3,3′-H2bpdc as a bridge and 2,2′-bpy as a terminal ligand. As expected, the 3,3′-bpdc2− anions bridge ZnII and CdII into a 1D zigzag single chain and 1D zigzag double chain, respectively. The 2,2′-bpy ligand serves as terminal components to decorate both sides of the 1D chain, which plays an important role in the self-assembly of the polymeric chain by providing potential supramolecular recognition sites for π–π stacking and C–H···π interactions. As a result, the two different zigzag chains in 1 and 2 are assembled into 2D wave-like layers via π–π stacking interactions. Furthermore, owing to the direction of the C–H···π interactions, the adjacent 2D layers embed into each other to form a 3D supramolecular framework. The thermogravimetric analysis and luminescent properties of 1 and 2 were also investigated. Two new 3D supramolecular embedded-frameworks based on 1D different-shaped coordination polymeric chains, have rationally synthesized and characterized. Moreover, the thermal stability and photoluminescence property of compounds 1 and 2 were also investigated.