Coordination polymers Zinc

Keywords coordination polymer, zinc (II) bromide, pyrazine... 

A polymeric structure can be generated by intermolecular coordination of a metalloporphyrin equipped with a suitable ligand. Fleischer (18,90) solved the crystal structure of a zinc porphyrin with one 4-pyridyl group attached at the meso position. In the solid state, a coordination polymer is formed (75, Fig. 30). The authors reported that the open polymer persists in solution, but the association constant of 3 x 104 M 1 is rather high, and it seems more likely, in the light of later work on closed macrocycles (see above), that this system forms a cyclic tetramer at 10-3 M concentrations in solution (71,73). 

Lewis-Acid Catalyzed. Recently, various Lewis acids have been examined as catalyst for the aldol reaction. In the presence of complexes of zinc with aminoesters or aminoalcohols, the dehydration can be avoided and the aldol addition becomes essentially quantitative (Eq. 8.97).245 A microporous coordination polymer obtained by treating anthracene- is (resorcinol) with La(0/Pr)3 possesses catalytic activity for ketone enolization and aldol reactions in pure water at neutral pH.246 The La network is stable against hydrolysis and maintains microporosity and reversible substrate binding that mimicked an enzyme. Zn complexes of proline, lysine, and arginine were found to be efficient catalysts for the aldol addition of p-nitrobenzaldehyde and acetone in an aqueous medium to give quantitative yields and the enantiomeric excesses were up to 56% with 5 mol% of the catalysts at room temperature.247... 

The ligand 2,5-bis(2-pyridyl)pyrazine was used in the synthesis of a range of zinc compounds to contrast with copper coordination polymers prepared with this ligand.169 Three zinc compounds were structurally characterized, [ZnCl2L(DMF)], [Zn3(OAc)6L2], and [Zn3Cl6L3] respectively a distorted square planar monomer, a linear trimer, and a triangular arrangement of zinc centers. 

The structure of coordination polymers formed with 3,6-bis(pyridin-3-yl)-l,2,4,5-tetrazine and zinc salts can be controlled by the choice of alcoholic solvents. Infinite lattice compounds of the form [Zn2L2(N03)4(Me0H)2(//-L)] and [Zn2(/U-L)3(N03)4](CH2C12)2) have been structurally characterized. The former structure shows an alternating single- and double-bridged species whereas the latter exists as a non-interpenetrated ladder complex.273... 

Zinc halide complexes with acetophenone have been structurally characterized and form monomeric or polymeric structural motifs.346 The bromide and iodide derivatives are monomeric and the chloride derivative is a coordination polymer with bridging chlorides. 

Zinc carboxylate interactions have been exploited as part of a fluorescent molecular sensor for uronic acids. The sensors feature two interactions coordination of the carboxylate to the zinc and a boronic acid diol interaction.389 Photoluminescent coordination polymers from hydrothermal syntheses containing Zn40 or Zn4(OH)2 cores with isophthalate or fumarate and 4,4 -bipyridine form two- and three-dimensional structures. Single X-ray diffraction of both dicarboxylates identified the network structure.373... 

Bis(but-3-enoato)zinc, a two-dimensional coordination polymer, has been polymerized in the solid state by irradiation of a crystalline sample resulting in isotactic zinc poly(but-3-enoate).393... 

The zinc complex of 1,1,1,5,5,5-hexafluoroacetylacetonate forms coordination polymers in reaction with either 2,5-bis(4-ethynylpyridyl)furan or l,2-bis(4-ethynylpyridyl)benzene. The X-ray crystal structures demonstrate an isotactic helical structure for the former and a syndio-tactic structure for the latter in the solid state. Low-temperature 1H and 19F NMR studies gave information on the solution structures of oligomers. Chiral polymers were prepared from L2Zn where L = 3-((trifluoromethyl)hydroxymethylene)-(+)-camphorate. Reaction with 2,5-bis(4-ethy-nylpyridyl)furan gave a linear zigzag structure and reaction with tris(4-pyridyl)methanol a homo-chiral helical polymer.479... 

The flexible ligand 4 can adopt different eonformations when it reacts with metal salts [51], For instance, ligand 4 reaeted with varied zinc(II) salts ZnX [X = (BF4)2, SO4, CI2, Br2,12] to afford a series of eoordination polymers with different structures. Coordination polymer [Zn(4)2](BF4)2 n (22) has an infinite 2D eationic double layered structure in which the ligand 4 has cis, cis, cw-eonformation, and the tetrafluoroborate anions are loeated in the voids of... 

Substituent Effect on the Structures OF Zinc 1,4-Benzenedicarboxylate Coordination Polymers Synthesized IN Dimethyl Sulfoxide... 

In order to explore the substituent effect on the assembly of coordination polymers, the influence of other factors should be excluded. Therefore the same synthetic condition as that for 1 was applied to synthesize the zinc 2,3,5,6-tetramethyl-1,4-benzenedicarboxylate, [Zn(tmbdc)(dmso)2] 2(DMSO) 2, except that H2bdc was replaced by H2tmbdc. [20]... 

Figure 2. Views of the structures of 1 (a) and 2 (b). The coordination polymers are shown in ball and stick mode, zinc ions are shown in polyhedra, DMSO solvent molecules are shown in CPK mode.

In conclusion, ID coordination polymer [Zn(tmbdc)(dmso)2]-2(DMSO) 2 has been synthesized with 2,3,5,6-tetramethyl-l,4-benzenedicarboxylic acid in DMSO. The structure contains ID chains formed by octahedraly coordinated Zn ions chelated by the carboxyl groups of tmbdc, rather than the 2D (4,4) nets constructed from paddle-wheel SBU of pairs Zn ions as found in [Zn2(bdc)2(dmso)2]-5DMSO 1. Analysis of the structure reveals that the steric hindrance of die four methyl groups of tmbdc determines the coordination environments of the zinc ions and the coordination modes of the carboxyls, and thus the final structures of the coordination polymers. The result also shows that DMSO is a stronger ancillary ligand and is also easier to be included in the structures of coordination polymers, compared to DMF. DMSO can be a better solvent for the syntheses of porous coordination polymers. 

Bis[(dimethylisopropoxysilyl)methyl]zinc (74) has proven to be a valuable reagent in the nickel-catalysed cross-coupling reactions with alkenylsulfoximines, giving allylic silanes with complete retention of configuration. An X-ray crystal structure determination of 74 showed this compound to exist in the solid state as a coordination polymer (Figure 41). In 74, in addition to the two covalent Zn—C bonds [Zn—C(l) 1.953(7)... 

EtZnI (117) behaves differently because no clear solutions of this compound could be obtained in apolar solvents. Crystals of 117 suitable for an X-ray crystal determination could be obtained by crystallization of crude 117 from EtI as a solvent . The solid state structure of 117 involves the packing of four EtZnI units in an orthorhombic unit cell in such a way that each of the zinc atoms has additional bonding interactions with two iodine atoms of neighbouring EtZnI units, thus forming a coordination polymer (Figure 57) . ... 

When 2-cyanoethylzinc iodide is recrystallized from THF, a crystalline material is obtained. This material appeared to be the mono-THF adduct of 2-cyanoethylzinc iodide which exists in the solid state as a coordination polymer via coordination of the cyanide functionality to an adjacent zinc atom. Coordination saturation at zinc is reached by the coordination of an additional THF molecule. No further structural data have been given for this compound . 

Functional Self-Assembled Zinc(II) Coordination Polymers... 

In 2003, we first used self-assembled zinc(II) terpyridine polymers in the fabrication of PLEDs.22 We synthesized a series of monomers containing two terpyridine as chelating units, which are at opposite ends and separated by a spacer group (R) (Fig. 5). The self-assembled zinc(II) coordination polymers were easily prepared by the addition of Zn(OAc)2 into solution of monomers. The product yields were up to 80%, and the inherent viscosities of the polymers were in the range of 0.48 to 1.21 dL/g, as determined using an Ubbelohde viscometer in NMP at 30 0.1 °C. 

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