Supramolecular Architecture from the Self-assembly of One-dimensionalCoordination Polymers and Hydrogen Bonds

The synthesis and characterization of coordination polymers have been a rapid growth area in recent years. The coordination polymers consist of 1D chains, 2D sheets or 3D networks in which metal-organic building blocks connected via coordinate and hydrogen bonds. They received considerable attention because of their versatile intriguing architectures, topologies and potential applications in materials1,2 . As rigid rod-like spacers, 4,4'-bipyridine and its analogues have been used to give r…     

3D Supramolecular Network Based on Hydrogen Bonds Between 1D [ Ni（μ2-C2O4） （ Him）2] Zigzag Chains

Introduction In recent years,considerable attention has been paid to supramolecular networks based on metal organic building blocks because of their potential applications in diverse fields,such as,catalysis,optics,sensors, magnetism,and molecular recognition[1-3].On the ba-     

A Porous 3D Supramolecular Architecture of Cd（II） Complex with Water Clusters as Pillars

A supramolecular complex of Cd（II） with 1D water tapes as pillars[Cd2（dpa）2（phen）2（H2O）2]·6H2O 1 （H2dpa = diphenic acid, phen = phenanthroline）, has been synthesized and characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray diffraction analysis. The crystal is of triclinic, space group P1^- with a = 9.7029（4）, b = 11.9601（5）, c = 12.1788（4） A, α = 71.6990（10）, β = 71.8740（10）, γ = 74.4680（10）°, V = 1252.39（8） A^3, C52H48Cd2N4O16, Mr = 1209.76, Z= 1, Dc = 1.604 g/cm^3,μ = 0.925 mm^-1, F（000） = 612, R = 0.0679 and wR = 0.2514 for 3870 observed reflections （I 〉 2σ（I））. Two intramolecular Cd（II） centers of this complex are encircled by two dpa^2- ligands forming an 18-membered ring, which is further assembled into a pillared three-dimensional （3D） supramolecular architecture through the synergetic effect of intermolecular face-to-face π…π stacking and weak O-H…O hydrogen-bonding interactions. Moreover, this complex exhibits photoluminescence with the main emission bands located at about 456 nm upon excitation at 355 nm in the solid state at room temperature.     

Distinct Hydrogen-bonded M^Ⅱ（H2O）8 Clusters as Second Building Units for 1-D, 2-D and 3-D Supramolecular Architectures （M = Cobalt and Nickel）

Two mononuclear metal-organic complexes, [Co（Hmpdc）2（H2O）4]·4H2O 1 and [Ni（Hfmpdc）2（H2O）4]·6H2O 2, were prepared from 2,6-dimethylpyridine-3,5-dicarboxylic acid （Hzmpdc） and 4-furyl-2,6-dimethylpyridine-3,5-dicarboxylic acid （H2fmpdc） with M（NO3）2 salts, respectively, and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectroscopy, and photoluminescent measurement. Complex 1 crystallizes in triclinic, space group P1 with a = 7.634（5）, b = 8.695（5）, c = 10.757（6）A, α = 69.647（7）, β = 69.957（8）, γ = 83.733（7）°, V = 628.9（7）A^3, Dc = 1. 561 g/cm^3,μ（MoKa） = 0.763 mm^-1, F（000） = 309, Z = 1, the final R = 0.0553 and wR = 0.1469 for 1909 observed reflections （Ⅰ 〉 2σ（Ⅰ））. Complex 2 crystallizes in monoclinic, space group P21/n with a = 9.5934（16）, b = 12.422（2）, c = 14.826（3） A, β = 105.201（2）°, V = 1705.0（5）A3, Dc = 1. 479 g/cm^3,μ（MoKa） = 0.655 mm^-1, F（000） = 796, Z = 2, the final R= 0.0351 and wR = 0.0889 for 2387 obsevved reflections （Ⅰ 〉 2σ（Ⅰ））. In the crystal structures of 1 and 2, diverse supramolecular motifs from 1-D chains/ladders to 3-D networks are constructed from corresponding distinct [M^Ⅱ（H2O）8] ion clusters as the second building units, respectively. The solid state compounds of 1 and 2 show similar photoluminescent spectra with emission maximum at ca.     

A 3-D Supramolecular Network with 1-D Cation Metal.organic Coordination Polymers and Diverse Motifs from Hydrogenbonded [M（H2O）4]-Carboxylates

One-pot solvothermal reaction of Iransition metal Znn salt with 4,4-bipyddyl （bpy） and 1,4-benzenediacrylic add （H2L） in the presence of Et3N generates a three-dimensional （3-D） supramolecular network with 1-D cation metal-organic coordination polymer, [Zn（H20）a（bpy）]-L 1, and structurally characterized by single-crystal X-ray diffraction, elemental analyses, IR spectroscopy, and photoluminescent property. The complex crystallizes in triclinic, space group P1 with a = 7.1291（2）, b = 7.3784（3）, c = 10.5042（3）A, α = 95.049（2）, β = 102.162（2）, 7 = 97.027（3）0, V= 532.38（3）A3, C22H24N2O8Zn, Mr = 509.82, De= 1.590 g/cm3, p（MoKa）= 1.207 ram-l, F（000） = 264, Z = 1,the finalR=O.0438and wR=O.lOll for 1589 observed reflections （I 〉 2σ（I））. In the crystal structure, the second building unit composed of [Zn（H2O）4].L constructs two distinct 2-D supramolecular sheets and a neutral 3-D architecture. The title compound 1 shows strong photoluminescence with emission maximum at 2 = 455 nm upon λex.max = 355 nm.     

Urothermal Synthesis and Crystal Structure of a Zn（Ⅱ） Coordination Polymer with a 3-D Supramolecular Structure

A new metal-organic coordination polymer [Zn(hfipbb)(e-urea)]n(1,H2hfipbb = 4,4'-(hexafluoroisopropylidene)bis(benzoic acid),e-urea = ethylene urea) has been urothermally synthesized and characterized by elemental analysis and single-crystal X-ray diffraction.The title complex crystallizes in monoclinic,space group P21/c with a = 13.302(4),b = 10.981(3),c = 13.804(4) ,β = 93.587(5)°,V = 2012.3(10) 3,C20H14N2O5F6Zn,Mr = 541.72,Z = 4,Dc = 0.447 g/cm3, = 0.328 mm-1,F(000) = 272,R = 0.0340 and wR = 0.1107 for 4528 observed reflections(I >2σ(I)).In the structure of compound 1,two Zn(Ⅱ) ions are bridged by two carboxylate groups from two hfipbb ligands to form a dinuclear unit,and each dinuclear Zn(Ⅱ) unit is linked with its two adjacent dinuclear units through four hfipbb ligands into an infinite one-dimensional double-chain.The interesting structural feature of compound 1 is that the one-D double-chains are self-interconnected into a three-D supramolecular structure through hydrogen bonds between the coordinated e-urea molecules and carboxylate oxygen atoms(N1 and O2,N2 and O4).     

Synthesis, Crystal Structure and Property of a Series of Supramolecular Polymers Based on Novel 3,5-Dimethyl- 2,6-bis（3-（pyrid-2-yl）-1,2,4-triazolyl）pyridine Ligand

Solvothermal reactions of 3,5-dimethyl-2,6-bis(3-(pyrid-2-yl)-1,2,4-triazolyl) pyridine (L), 1,4-benzendicarboxylic acid (H2bdc), and transitional metal cations of MII (M = Mn, Co, Cd) in the presence of oxalic acid (H2ox) afford three novel supramolecular polymers (CPs), namely, {[M2(ox)(L)2][bdc][M2(Hox)2(OH)2(H2O)4].3H2O}n (M=Mn for 1, Co for 2, Cd for 3). Single-crystal X-ray diffraction analysis reveals that complexes 1-3 are isostructural and the 3D supramolecular structure was connected through non-covalent interactions. With the help of H2ox, the L ligands cheated with center atoms forming a butterfly [M2(ox)(L)2]2+ building block. The bdc2- ligand linked with the unprecedented [M2(Hox)2(OH)2(H2O)4] units through strong O-H…O hydrogen bonds forming a zigzag chain, which are further connected through π…π interactions between L and bdc2- ligands to form a 3D supramolecular structure. Moreover, elemental analyses, IR, thermogravimetric, PXRD and luminescence have been investigated.     

Two New Organic Supramolecular Complexes Based on 2,3,6,7-Tetrahydroxyl-9,10-dimethyl-9,10-dihydro-9,10-ethanoanthracene and 4,4′-Bipyridine or 4,4′-Bipyridinylethane

Two new organic supramolecular cocrystal complexes C18H18O4·C10H8N2(I) and C18H18O4·C12H10N2(II)(C18H18O4 = 2,3,6,7-tetrahydroxyl-9,10-dimethyl-9,10-dihydro-9,10-ethanoanthracene(LH4), C10H8N2 = 4,4'-bipyridine(bpy) and C12H10N2 = 4,4'-bipyridinylethane(bpe)) have been obtained by mixing LH4 with corresponding bpy or bpe ligand. The two complexes have been determined by X-ray crystal structure analysis, elemental analysis and IR analysis. Compound I crystallizes in the orthorhombic Pnma with a = 9.7078(4), b = 22.4974(10), c = 20.6272(9) V = 4505.0(3)3, Mr = 454.51, Dc. = 1.340 g·cm-3, μ = 0.09 mm-1, F(000) = 1920, Z = 8, R = 0.0503 and wR = 0.1360. Compound II crystallizes in monoclinic C2/c with a = 29.944(6), b = 9.820(2), c = 22.643(5) , V = 5048.4(18)3, Mr = 480.54, Dc. = 1.265 g cm–3, μ = 0.084 mm–1, F(000) = 2032, Z = 8, R = 0.0548 and wR = 0.1600. X-ray single-crystal structure analysis shows that two-dimensional(2D) layer supramolecular structures are formed through hydrogen bonds and π-π interactions in the two complexes. IR analysis also indicates that there are only associated hydroxyl groups in the two complexes.     

Synthesis and Supramolecular Structure of Chloro（1,10-phenanthroline ）copper（I） Hexahydrate

1INTRODUCTION Atom transfer radical addition is an efficient me-thod for carbon-carbon bond formation in organic synthesis[1,2].In some of these reactions,a transi-tion-metal catalyst acts as a carrier of the halogen atom in a reversible redox process.The transition-metal-catalyzed has been successfully used to con-trol radical polymerization[3].In the process,the transition-metal species initially abstracts halogen atom X from organic halide to form oxidized species and carbon-centered r…     

A Robust Nanoporous Supramolecular Metal–Organic Framework Based on Ionic Hydrogen Bonds

Hydrogen‐bond assembly of tripod‐like organic cations [H₃‐MeTrip]³⁺ (1,2,3‐tri(4′‐pyridinium‐oxyl)‐2‐methylpropane) and the hexa‐anionic complex [Zr₂(oxalate)₇]^6? leads to a structurally, thermally, and chemically robust porous 3D supramolecular framework showing channels of 1 nm in width. Permanent porosity has been ascertained by analyzing the material at the single‐crystal level during a sorption cycle. The framework crystal structure was found to remain the same for the native compound, its activated phase, and after guest resorption. The channels exhibit affinities for polar organic molecules ranging from simple alcohols to aniline. Halogenated molecules and I₂ are also taken up from hexane solutions by this unique supramolecular framework.     

Aromatic Embrace Motifs for Bulk Supramolecular Polymers

Frequently encountered in crystalline materials, aromatic embraces (AEs) are formed when arylated molecules interact through multiple concerted aromatic interactions. AEs are a robust motif that is suitable for the preparation of amorphous bulk supramolecular polymers (BSPs). Crystal engineering revealed that the polymorphic compound (PPh₃)(Cp)Fe(CO){CO(CH₂)₅CH₃} (Cp=cyclopentadienyl), known as FpC₆, assembled into various chain structures through several AE motifs. Upon melting, FpC₆ always adopted the same AE motif, which extended into the corresponding embracing “ladder” chains. The resultant BSP displayed typical polymer behaviour, including the presence of a glass transition and viscoelasticity, which allowed the effect of thermal history on the polymerisation behaviour to be explored. The ladder chains formed by the AE remain assembled at temperatures of up to 130 °C and were able to effectively suppress crystallisation during cooling. The ability of the AE to form chains at high temperatures and suppress crystallisation is a new opportunity to advance the field of BSPs and supramolecular chemistry.     

Crossed Ladders in a 2-D Mixed-ligand Lanthanide Coordination Polymer:Synthesis,Crystal Structure and Photoluminescence

A new metal-organic coordination polymer,[Ce(L 1)(L 2)(H 2 O)]·2H 2 O (1,H 2 L 1=2,6-dimethylpyridine-3,5-dicarboxylic acid,H 2 L 2=(E)-2,6-dimethyl-4-styrylpyridine-3,5-dicer-boxylic acid),has been synthesized and characterized by elemental analysis,IR,and X-ray single-crystal diffraction.Compound 1 crystallizes in triclinic,space group P1 and displays a two-dimensional coordination network structure.In 1,the relatively rare crossed ladders cons-tructed by mixed ligands organize a 2-D grid with the topology of (4 2 6) 2 (4 8 6 6 8),and the layers further build up a 3-D supramolecular architecture via interlaminar hydrogen bonds.     

Supramolecular Terbium-SIP Complex Pillared by 4,4＇-Bipyridyl, {[Tb（SIP）（H2O）5]2（bpy）3（H2O）}n： Synthesis,Crystal Structure and Photoluminescence

The supramolecular terbium complex, {[Tb（SIP）（H2O）5]2（bpy）3（H2O）}n （NaH2SIP = 5-sulfoisophthalic acid monosodium salt and bpy = 4,4＇-bipyridyl）, has been synthesized by the hydrothermal reaction of Tb4O7 with NaH2SIP and bpy at 165 ℃, and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectrum, powder X-ray diffraction and photoluminescence spectrum. It crystallizes in a monoclinic system, space group C2/c, with a = 30.6840（1）, b = 10.9206（2）, c = 17.4967（3） A, β= 111.931（1）°, V = 5438.65（14） A^3, Z = 4, C46H52N6O25S2Tb2, Mr = 1470.90, Dc = 1.796 g/cm^3, p = 2.747 mm^-1, F（000） = 2928, the final R = 0.0654 and wR = 0.1322 for 3806 observed reflections with I 〉 2σ（I）. In the neutral [Tb（SIP）（H2O）5]2 motif, the Tb（III） ions are linked by the SIP ligands to form a one-dimensional zigzag chain propagating along the c axis. The zigzag chains are linked together by hydrogen bonds and π-π stacking interactions to form a two-dimensional supramolecular framework. The uncoordinated bpy molecules act as pillars to extend the two-dimensional sheets into a distinctive pillared three-dimensional supramolecular structure through O-H...N hydrogen bonds. The photoluminescence of the complex was investigated at room temperature in the solid state.     

Supramolecular Terbium-SIP Complex Pillared by 4,4'-Bipyridyl,{[Tb(SIP)(H_2O)_5]_2(bpy)_3(H_2O)}n:Synthesis,Crystal Structure and Photoluminescence

The supramolecular terbium complex, {[Tb(SIP)(H2O)5]2(bpy)3(H2O)}n (NaH2SIP= 5-sulfoisophthalic acid monosodium salt and bpy=4,4'-bipyridyl), has been synthesized by the hydrothermal reaction of Tb4O7 with NaH2SIP and bpy at 165 ℃, and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectrum, powder X-ray diffraction and photoluminescence spectrum. It crystallizes in a monoclinic system, space group C2/c, with a= 30.6840(1), b=10.9206(2), c=17.4967(3), β=111.931(1)o, V=5438.65(14)3, Z=4, C46H52N6O25S2Tb2, Mr=1470.90, Dc=1.796 g/cm3, μ=2.747 mm-1, F(000)=2928, the final R= 0.0654 and wR=0.1322 for 3806 observed reflections with I > 2σ(I). In the neutral [Tb(SIP)(H2O)5]2 motif, the Tb(III) ions are linked by the SIP ligands to form a one-dimensional zigzag chain propagating along the c axis. The zigzag chains are linked together by hydrogen bonds and π-π stacking interactions to form a two-dimensional supramolecular framework. The uncoordinated bpy molecules act as pillars to extend the two-dimensional sheets into a distinctive pillared three-dimensional supramolecular structure through O-H···N hydrogen bonds. The photoluminescence of the complex was investigated at room temperature in the solid state.     

A Phosphorescent Platinum(II) Bipyridyl Supramolecular Polymer Based on Quadruple Hydrogen Bonds

A platinum(II) bipyridyl complex bearing bis‐ureidopyrimidinone (Pt‐bisUPy) has been designed and its self‐assembling behavior has been thoroughly investigated by ¹H NMR, DOSY NMR, Ubbelohde viscometry analysis, UV/Vis, and emission spectroscopies. Pt‐bisUPy underwent concentration‐dependent ring‐chain polymerization in apolar solvents. Hydrogen‐bonding interactions play an important role during the formation of the supramolecular polymers. Hydrogen‐bonded supramolecular polymers were transformed to nanoparticles in water through the miniemulsion method. These nanoparticles showed strong π–π excimeric emission. Metal‐metal‐to‐ligand charge transfer (MMLCT) from Pt–Pt interactions was not significant in the emission spectrum. The phosphorescence of the nanoparticle persisted even under aerobic conditions. The triplet state of these phosphorescent nanomaterials were long‐lived and possessed moderate emission quantum yields. Furthermore, the low toxicity of these materials promises a place for them in in vitro and in vivo bioimaging.     

Thioamides: Versatile Bonds To Induce Directional and Cooperative Hydrogen Bonding in Supramolecular Polymers

The amide bond is a versatile functional group and its directional hydrogen‐bonding capabilities are widely applied in, for example, supramolecular chemistry. The potential of the thioamide bond, in contrast, is virtually unexplored as a structuring moiety in hydrogen‐bonding‐based self‐assembling systems. We report herein the synthesis and characterisation of a new self‐assembling motif comprising thioamides to induce directional hydrogen bonding. N,N′,N′′‐Trialkylbenzene‐1,3,5‐tris(carbothioamide)s (thioBTAs) with either achiral or chiral side‐chains have been readily obtained by treating their amide‐based precursors with P₂S₅. The thioBTAs showed thermotropic liquid crystalline behaviour and a columnar mesophase was assigned. IR spectroscopy revealed that strong, three‐fold, intermolecular hydrogen‐bonding interactions stabilise the columnar structures. In apolar alkane solutions, thioBTAs self‐assemble into one‐dimensional, helical supramolecular polymers stabilised by three‐fold hydrogen bonding. Concentration‐ and temperature‐dependent self‐assembly studies performed by using a combination of UV and CD spectroscopy demonstrated a cooperative supramolecular polymerisation mechanism and a strong amplification of supramolecular chirality. The high dipole moment of the thioamide bond in combination with the anisotropic shape of the resulting cylindrical aggregate gives rise to sufficiently strong depolarised light scattering to enable depolarised dynamic light scattering (DDLS) experiments in dilute alkane solution. The rotational and translational diffusion coefficients, D_trans and D_rot, were obtained from the DDLS measurements, and the average length, L, and diameter, d, of the thioBTA aggregates were derived (L=490 nm and d=3.6 nm). These measured values are in good agreement with the value L_w=755 nm obtained from fitting the temperature‐dependent CD data by using a recently developed equilibrium model. This experimental verification validates our common practice for determining the length of BTA‐based supramolecular polymers from model fits to experimental CD data. The ability of thioamides to induce cooperative supramolecular polymerisation makes them effective and broadly applicable in supramolecular chemistry.     

Distinct Hydrogen-bonded MII(H2O)8 Clusters as Second Building Units for 1-D, 2-D and 3-D Supramolecular Architectures (M = Cobalt and Nickel)

Two mononuclear metal-organic complexes, [Co(Hmpdc)2(H2O)4]·4H2O 1 and [Ni(Hfmpdc)2(H2O)4]·6H2O 2, were prepared from 2,6-dimethylpyridine-3,5-dicarboxylic acid (H2mpdc) and 4-furyl-2,6-dimethylpyridine-3,5-dicarboxylic acid (H2fmpdc) with M(NO3)2 salts, respectively, and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectroscopy, and photoluminescent measurement. Complex 1 crystallizes in triclinic, space group P with a = 7.634(5), b = 8.695(5), c = 10.757(6)(A), α = 69.647(7), β = 69.957(8), γ = 83.733(7)°, V = 628.9(7)(A)3, Dc = 1. 561 g/cm3, μ(MoKα) = 0.763 mm-1, F(000) = 309, Z = 1, the final R = 0.0553 and wR = 0.1469 for 1909 observed reflections (I > 2σ(I)). Complex 2 crystallizes in monoclinic, space group P21/n with a = 9.5934(16), b = 12.422(2), c = 14.826(3)(A), β = 105.201(2)°, V = 1705.0(5)(A)3, Dc = 1. 479 g/cm3, μ(MoKα) = 0.655 mm-1, F(000) = 796, Z = 2, the final R = 0.0351 and wR = 0.0889 for 2387 observed reflections (I > 2σ(I)). In the crystal structures of 1 and 2, diverse supramolecular motifs from 1-D chains/ladders to 3-D networks are constructed from corresponding distinct [MⅡ(H2O)8] ion clusters as the second building units, respectively. The solid state compounds of 1 and 2 show similar photoluminescent spectra with emission maximum at ca. 466 nm at room temperature.