scholarly journals A Proposal for Positive Cooperativity in Anion−Cation Binding in Yttrium and Lutetium Complexes Based ono-Amino-Substituted Phenolate Ligands. On the Way to Coordination Polymers by Self-Assembly. Molecular Structures of [ClLu(OAr)3Na] (X-ray) and [ClY(OAr‘)3Y(OAr‘)3Na] (X-ray and89Y-NMR)

1996 ◽  
Vol 35 (5) ◽  
pp. 1185-1194 ◽  
Author(s):  
Marinus P. Hogerheide ◽  
Stéphanie N. Ringelberg ◽  
David M. Grove ◽  
Johann T. B. H. Jastrzebski ◽  
Jaap Boersma ◽  
...  
Keyword(s):  
Coordination Polymers ◽  
Self Assembly ◽  
Cation Binding ◽  
Molecular Structures ◽  
X Ray ◽  
Positive Cooperativity ◽  
Phenolate Ligands ◽  
The Way

A new twofold interpenetrated two-dimensional cadmium(II) coordination polymer constructed from 2,2′-(benzene-1,4-dicarboxamido)dipropionate

2018 ◽  
Vol 74 (11) ◽  
pp. 1434-1439
Author(s):  
Hong-Tao Zhang ◽  
Xiao-Long Wang
Keyword(s):  
Coordination Polymer ◽  
Coordination Polymers ◽  
Self Assembly ◽  
Fluorescence Emission ◽  
Functional Materials ◽  
Two Dimensional ◽  
X Ray Diffraction ◽  
X Ray ◽  
Carboxylate Groups ◽  
Potential Applications

In recent years, much initial interest and enthusiasm has focused on the self-assembly of coordination polymers due to the aesthetics of their crystalline architectures and their potential applications as new functional materials. As part of an exploration of chiral coordination polymers, a new twofold interpenetrated two-dimensional (2D) coordination polymer, namely, poly[[tetraaquabis[μ3-(2R,2′R)-2,2′-(benzene-1,4-dicarboxamido)dipropionato-κ5 O,O′:O′′,O′′′:O′′]dicadmium(II)] trihydrate], {[Cd2(C14H14N2O6)2(H2O)4]·3H2O} n , has been synthesized by the reaction of Cd(CH3COO)2·2H2O with the designed ligand (2R,2′R)-2,2′-(benzene-1,4-dicarboxamido)dipropionic acid (H2 L). The compound has been structurally characterized by elemental analysis, IR spectroscopy, powder X-ray diffraction and single-crystal X-ray diffraction analysis. In the crystal structure, each CdII cation binds to three carboxylate groups from two crystallographically independent L 2− dianions. Four carboxylate groups link two crystallographically independent cadmium cations into a 4,4-connected secondary building unit (SBU). The resulting SBUs are extended into a two-dimensional folding sheet via the terephthalamide moiety of the ligand as a spacer, which can be simplified as a (4,4)-connected 4,4L15 net with the point symbol (3.53.62)(32.52.62). In the lattice, two independent folding sheets interpenetrate each other to yield a double-sheet layer. The resulting 2D layers pack in parallel arrays through intermolecular hydrogen bonds and interlayer π–π interactions. The thermal stability and photoluminescence properties of the title compound have been investigated and it exhibits an enhanced fluorescence emission and a longer lifetime compared with free H2 L.

Hydrothermal Syntheses, Crystal Structures, and Luminescent Properties of Two MnII Coordination Polymers: From Two-Fold Interpenetrated pcu Topological Net to Polycatenated 2D+2D→3D Framework

2015 ◽  
Vol 68 (2) ◽  
pp. 322 ◽  
Author(s):  
Wenlong Liu ◽  
Mengqiang Wu ◽  
Xueying Wang ◽  
Wei Wang ◽  
Dayu Liu ◽  
...  
Keyword(s):  
Dicarboxylic Acid ◽  
Coordination Polymers ◽  
Self Assembly ◽  
Room Temperature ◽  
Luminescent Properties ◽  
The Self ◽  
X Ray Diffraction ◽  
X Ray ◽  
3D Framework ◽  
Dimethyl Benzene

Using a hydrothermal synthesis, the self-assembly of MnII ions and 1,4-bis(1-imidazol-yl)-2,5-dimethyl benzene with two dicarboxylate ligands, 2-nitrobenzene-1,4-dicarboxylic acid (2-H2ata) and 5-methylbenzene-1,3-dicarboxylic acid (5-CH3-H2ip) constructed two interesting coordination polymers: [Mn(2-ata)(bimb)]n (1) and {[Mn(5-CH3-ip)(bimb)1.5]·2H2O}n (2), where bimb refers to 1,4-bis(1-imidazol-yl)-2,5-dimethyl benzene. Their structures were determined by single-crystal X-ray diffraction, elemental analysis, and infrared spectroscopy. Complex 1 exhibits a 2-fold interpenetrated pcu net. Complex 2 shows an unusual polycatenated 2D+2D→3D framework. In addition, the solid-state photoluminescent properties of 1 and 2 were investigated at room temperature.

New homodinuclear tris(3-alkylpyrazolyl)borate complexes of CoIIand NiIIwith a tetraacetylethane dianion as a bridging ligand

2016 ◽  
Vol 72 (11) ◽  
pp. 777-785
Author(s):  
Elena A. Mikhalyova ◽  
Swiatoslaw Trofimenko ◽  
Matthias Zeller ◽  
Anthony W. Addison ◽  
Vitaly V. Pavlishchuk
Keyword(s):  
Metal Ions ◽  
Coordination Polymers ◽  
Metal Ion ◽  
Molecular Structures ◽  
Polynuclear Complexes ◽  
X Ray ◽  
X Ray Crystallography ◽  
Coordination Sites ◽  
Borate Complexes ◽  
Capping Ligands

Polynuclear complexes and coordination polymers of 3dmetals have attracted significant interest evoked by a number of their unique properties. One of the most common approaches to the directed synthesis of coordination polymers is the linking of pre-prepared discrete coordination units by polydentate ligands. The formation of polynuclear complexes is usually a spontaneous process and precise prediction of the products of such reactions is virtually impossible in most cases. Tris(pyrazolyl)borates (Tp) act as tripodal `capping' ligands which form stable complexes with 3dmetal ions. In such 1:1 compounds, three metal-ion coordination sites are occupied by N atoms from a Tp anion. This limits the number of remaining coordination sites, and thus the number of additional ligands which may coordinate, and opens an attractive approach for the directed design of desirable structures by exploiting ligands with appropriate composition and topology. In the present study, Tp anions with neopentyl [TpNp, tris(3-neopentylpyrazolyl)borate] and cyclohexyl [TpCy, tris(3-cyclohexylpyrazolyl)borate] substituents were used as `capping' ligands and the dianion of tetraacetylethane (3,4-diacetylhexa-2,4-diene-2,5-diolate, tae2−) was employed as a bridge. The dinuclear complexes (μ-3,4-diacetylhexa-2,4-diene-2,5-diolato-κ4O2,O3:O4,O5)bis{[tris(3-cyclohexyl-1H-pyrazol-1-yl-κN2)borato]cobalt(II)} acetonitrile disolvate, [Co2(C27H40BN6)2(C10H12O4)]·2CH3CN, (I)·2CH3CN, and (μ-3,4-diacetylhexa-2,4-diene-2,5-diolato-κ4O2,O3:O4,O5)bis{[tris(3-neopentyl-1H-pyrazol-1-yl-κN2)borato]nickel(II)}, [Ni2(C24H40BN6)2(C10H12O4)], (II), were synthesized by the reaction of the mononuclear complexes TpCyCoCl or TpNpNiCl with H2tae (3,4-diacetylhexane-2,5-dione or tetraacetylethane) in the presence of NEt3as base. Compounds (I) and (II) were characterized by mass spectrometry, elemental analysis, and X-ray crystallography. They possess similar molecular structures, X-ray diffraction revealing them to be dinuclear in nature and composed of discrete Tp–Munits in which two metal ions are linked by a tae2−dianion. Each metal ion possesses a five-coordinate square-pyramidal environment. The interplanar angles between the acetylacetonate fragments are significantly smaller than the near-90° values commonly observed.

Self Assembly of Anisotropic Organic Molecules: Diffusion versus Sticking Anisotropy

2005 ◽  
Vol 901 ◽  
Author(s):  
Stephen Berkebile ◽  
Georg Koller ◽  
Gregor Hlawacek ◽  
Martin Oehzelt ◽  
Roland Resel ◽  
...  
Keyword(s):  
Growth Kinetics ◽  
Self Assembly ◽  
Molecular Orientation ◽  
Elevated Temperatures ◽  
Film Growth ◽  
Building Blocks ◽  
Molecular Structures ◽  
Ex Situ ◽  
Diffusion Anisotropy ◽  
X Ray

AbstractThe molecular/crystal orientation and morphology of active molecular structures is a key determinant for the function of nanoscaled organic devices. In π-conjugated systems, both charge transport and optical properties will strongly depend on the molecular orientation due to the highly anisotropic charge carrier mobility in these organic crystals and the anisotropic absorption and luminescence behavior of the molecules. Although the importance of organic on inorganic interface formation and thin film growth is widely acknowledged, little is known regarding the growth kinetics. A better understanding of the processes driving molecular self-assembly is necessary if the self-assembly process is to be controlled. Moreover, it is interesting as the anisotropy of the molecular building blocks presents a fundamental difference from what is known from inorganic growth. Here we show that either sticking or diffusion anisotropy can control the growth depending on preparation conditions. This is illustrated by an investigation into the growth of sexiphenyl (6P) on the anisotropic TiO2(110)-(1×1) surface for temperatures between 80K and 400K using in-situ UHV photoemission, x-ray absorption spectroscopy, synchrotron x-ray diffraction and ex-situ atomic force microscopy. For 6P adsorption even at 80K we found that the molecules orient parallel to the TiO2 oxygen rows and form small crystallites. At 300K this molecular orientation is retained and large micrometer sized 6P(203) oriented needles running perpendicular to oxygen substrate rows are formed. In contrast, for growth at elevated temperatures the 6P molecular axis is near perpendicular to the surface and large islands elongated parallel to the substrate rows are formed. These differences in crystallite orientation and morphology can be explained by the domination of the growth kinetics by either sticking or diffusion anisotropy depending on growth temperature.

Self-Assembly Of 1D- And 3D-Networks Through Non-Coordination Intermolecular Forces: Synthesis And Crystal Structures Of Copper(I) Complexes Based On Pyridazine-Type Ligands

2007 ◽  
Vol 62 (6) ◽  
pp. 799-806 ◽  
Author(s):  
Laurent Plasseraud ◽  
Andreas Scheurer ◽  
Frank Hampel
Keyword(s):  
Solid State ◽  
Self Assembly ◽  
Three Dimensional ◽  
Intermolecular Forces ◽  
Molecular Structures ◽  
Dinuclear Complexes ◽  
Stacking Interactions ◽  
The Novel ◽  
X Ray ◽  
3D Networks

Reaction of [Cu2(H3CCN)2(μ-pydz)3][PF6]2 (1) with an excess of pyridazine or phthalazine yielded the novel dinuclear complexes [Cu2(μ-pydz)3(pydz)2][PF6]2 (2) and [Cu2 (μ- pydz)(μ-phtz)2(phtz)2][PF6]2 (5), respectively. Depolymerisation of the coordination polymer 1∞ {[Cu(μ-pydz)2][PF6]} (3) in dichloromethane by addition of an excess of benzo[c]cinnoline afforded the dinuclear copper(I) salt [Cu2(μ-pydz)2(pydz)2(benzo[c]cinnoline)2][PF6]2 (4). Furthermore, a new route for the preparation of bis(benzonitrile)tris(μ-phthalazine)dicopper(I) bis(trifluoromethanesulfonate), [Cu2(C6H5CN)2(μ-phtz)3][CF3SO3]2 (7), was established from {[Cu(CF3SO3)]2 ・C6H5Me}, phthalazine and benzonitrile via the very air-sensitive intermediate [Cu2(CF3SO3)2(μ-phtz)3] (6). Copper(I) compounds 2, 4, and 7 were completely characterised and the molecular structures confirmed in the solid state by single-crystal X-ray structure determination. The analysis of the packing of the molecules in crystals of 4 and 7 revealed a self-assembly of oneand three-dimensional frameworks, respectively, resulting from intermolecular π-π stacking interactions between pyridazine-type ligands

Flexibility in the Self-Assembly of Silver Complexes: Coordination Polymers from Multi-Armed Pyridylmethyleneoxy Ligands

2013 ◽  
Vol 66 (4) ◽  
pp. 443 ◽  
Author(s):  
Peter J. Steel ◽  
Christopher M. Fitchett
Keyword(s):  
Coordination Polymers ◽  
Self Assembly ◽  
Pyridine Ring ◽  
Relative Orientation ◽  
The Self ◽  
Silver Complexes ◽  
X Ray ◽  
Precise Nature ◽  
X Ray Crystallography

The syntheses of new silver complexes of five isomeric bis(pyridylmethyleneoxy)benzenes, differing in the position of substitution on the benzene and pyridine rings, and three isomeric 1,3,5-tris(pyridylmethyleneoxy)benzenes, differing in the position of substitution on the pyridine ring, are described. The structures of six of these complexes were characterised using X-ray crystallography, showing the formation of coordination polymers for 3-pyridyl- and 4-pyridyl-armed ligands and discrete complexes for 2-pyridyl-armed ligands. The precise nature of the structure was further determined by the relative orientation of the pyridine rings in each case.

scholarly journals Crystal Engineering of Schiff Base Zn(II) and Cd(II) Homo- and Zn(II)M(II) (M = Mn or Cd) Heterometallic Coordination Polymers and Their Ability to Accommodate Solvent Guest Molecules

Molecules ◽  
2021 ◽  
Vol 26 (8) ◽  
pp. 2317
Author(s):  
Olga Danilescu ◽  
Paulina N. Bourosh ◽  
Oleg Petuhov ◽  
Olga V. Kulikova ◽  
Ion Bulhac ◽  
...  
Keyword(s):  
Schiff Base ◽  
Coordination Polymers ◽  
Crystal Engineering ◽  
Self Assembly ◽  
X Ray Diffraction ◽  
Guest Molecules ◽  
X Ray ◽  
1D Chain ◽  
Two Temperatures ◽  
Adsorption Desorption

Based on solvothermal synthesis, self-assembly of the heptadentate 2,6-diacetylpyridine bis(nicotinoylhydrazone) Schiff base ligand (H2L) and Zn(II) and/or Cd(II) salts has led to the formation of three homometallic [CdL]n (1), {[CdL]∙0.5dmf∙H2O}n (2) and {[ZnL]∙0.5dmf∙1.5H2O}n (3), as well as two heterometallic {[Zn0.75Cd1.25L2]∙dmf∙0.5H2O}n (4) and {[MnZnL2]∙dmf∙3H2O}n coordination polymers. Compound 1 represents a 1D chain, whereas 2–5 are isostructural and isomorphous two-dimensional structures. The entire series was characterized by IR spectroscopy, thermogravimetric analysis, single-crystal X-ray diffraction and emission measurements. 2D coordination polymers accommodate water and dmf molecules in their cage-shaped interlayer spaces, which are released when the samples are heated. Thus, three solvated crystals were degassed at two temperatures and their photoluminescent and adsorption–desorption properties were recorded in order to validate this assumption. Solvent-free samples reveal an increase in volume pore, adsorption specific surface area and photoluminescence with regard to synthesized crystals.

Synthesis and structure of iron(III) complexes of amine-bis(phenolate) ligands

2014 ◽  
Vol 92 (8) ◽  
pp. 758-764 ◽  
Author(s):  
Elliott F. Chard ◽  
John R. Thompson ◽  
Louise N. Dawe ◽  
Christopher M. Kozak
Keyword(s):  
Single Crystal ◽  
Molecular Structures ◽  
Tridentate Ligand ◽  
Lithium Salts ◽  
X Ray ◽  
Trigonal Bipyramidal ◽  
Phenolate Ligands ◽  
Tetrahedral Iron

The synthesis and structures of four new iron(III) amine-bis(phenolate) complexes are reported. Reaction of anhydrous FeCl3 with the diprotonated tridentate ligand isopropyl-N,N-bis(2-methylene-4-t-butyl-6-methylphenol) (H2L1) and NEt3 produces the trigonal bipyramidal iron(III) complex [NEt3H]+ [FeCl2L1]– (1). The reaction of FeBr3 with the sodium or lithium salts, Na2L1 and Li2L2, results in the formation of FeBr2L1H (2) and FeBr2L2H (3), tetrahedral iron(III) complexes possessing two bromide ligands and quaternized ammonium fragments. A trigonal bipyramidal FeIII hydroxido-bridged dimer, [Fe(μ-OH)L2]2 (4), was also isolated during the synthesis of 3. Single-crystal X-ray molecular structures have been determined for complexes 1–4 and H2L2.

scholarly journals Synthesis, Structure, and Properties of Coordination Polymers Based on 1,4-Bis((2-methyl-1H-imidazol-1-yl)methyl)benzene and Different Carboxylate Ligands

Crystals ◽  
2018 ◽  
Vol 8 (7) ◽  
pp. 288 ◽  
Author(s):  
Kang Liu ◽  
Yaowen Zhang ◽  
Liming Deng ◽  
Shaoshao Jiao ◽  
Zhenyu Xiao ◽  
...  
Keyword(s):  
Hydrogen Bonding ◽  
Coordination Polymers ◽  
Self Assembly ◽  
3D Structure ◽  
X Ray Diffraction ◽  
Single Chain ◽  
X Ray ◽  
Mixed Ligands ◽  
Pyrazinecarboxylic Acid ◽  
Methyl Benzene

Three novel coordination polymers, formulated as {[Zn(1,4-bmimb)(PhAA)2]·H2O}n (1), [Cu(1,4-bmimb)0.5(2,6-PyDC)]n (2), and {[Cu(1,4-bmimb)0.5(2-PAC)(HCOO)]·2H2O}n (3) (1,4-bmimb = 1,4-bis((2-methyl-1H-imidazol-1-yl)methyl)benzene; PhAA = phenylacetic acid; 2,6-PyDC = pyridine-2,6-dicarboxylic acid; 2-PAC = 2-pyrazinecarboxylic acid), were synthesized by the self-assembly of mixed ligands with Zn(II) and Cu(II) under solvothermal conditions and characterized by means of single-crystal X-ray diffraction, X-ray powder diffraction, infrared spectra, thermogravimetric analysis, fluorescence spectra and UV-vis absorption spectra. 1 is shown as a Z-shaped chain, which is formed by Zn2+, PhAA ligands, and 1,4-bmimb ligands, and is assembled into a 3D structure by hydrogen bonding and π···π interaction. Similarly, 2 displays a single chain, which is built by Cu2+, 2,6-PyDC ligands, and 1,4-bmimb ligands, and is assembled into a 3D structure by hydrogen bonding and π···π interaction. 3 possesses a 1D ladder structure, which is formed by Cu2+, 2,6-PyDC ligands, and 1,4-bmimb ligands, and is assembled into a 3D structure by hydrogen bonding. The luminescence properties (for 1) and UV-vis spectrum (for 2 and 3) were also studied and discussed.

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