Zinc dicarboxylate polymers and dimers: thiourea substitution as a tool in supramolecular synthesis

Burke, Nichola J.; Burrows, Andrew D.; Donovan, Adele S.; Harrington, Ross W.; Mahon, Mary F.; Price, Caroline E.

doi:10.1039/b307420j

Cited by 36 publications

(13 citation statements)

References 23 publications

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“…The Zn···Zn distances are 6.80 and 6.92 Å for the two chains, shorter than those in 7Ϫ9, and clearly illustrate the effect of the intrachain hydrogen bonding. This becomes more apparent when comparing the chains in 10 with those observed in [Zn{SC(NHMe)(NH 2 )} 2 (µ-1,3-phenylenediacetate)] n , [21] as in this latter compound, substitution of a hydrogen atom for a methyl group prevents the extended intrachain hydro- gen bonding from occurring. Consequently, the Zn···Zn separation is much larger (11.6 Å ).…”

Section: Syntheses Of Compounds 7؊11mentioning

confidence: 82%

“…No evidence for thiourea-containing polymers was obtained for this reaction, which is surprising as coordination polymers containing the substituted thioureas MeNHC(S)NH 2 and MeNHC(S)NHMe have been prepared in good yield and structurally characterised. [21] The reaction of [Zn(tu) 4 ]Cl 2 with sodium fumarate was previously reported to give [Zn(tu) 2 (µ-fumarate)] n (1), [14] and this reaction was repeated to confirm 1 as the only product by X-ray powder diffraction. In contrast, the reac- Like mesaconate, fumarate has a trans orientation around the central double bond, and as such the two carboxylate groups are co-planar.…”

Section: Reactions Of [Zn(tu) 4 ](No 3 ) 2 With Dicarboxylatesmentioning

confidence: 99%

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Backbone Flexibility and Counterion Effects on the Structure and Thermal Properties of Di(thiourea)zinc Dicarboxylate Coordination Polymers

et al. 2004

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The reaction between [Zn(tu) 4 ]Cl 2 and the appropriate sodium dicarboxylate has been shown to give the coordination polymers [Zn(tu) all of which have been crystallographically characterised. The crystal structures of 7−9 demonstrate that these compounds form helical structures in which the dicarboxylates adopt conformations with the relative positions of the carboxylate groups similar to those in constrained anions such as phthalate. The role of the chloride counterion in the starting material has been explored by investigating the reactions of [Zn(tu) 4 ](NO 3 ) 2 with a range of dicarboxylates. Although in the majority of cases the counterion was shown to have no

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Section: Syntheses Of Compounds 7؊11mentioning

confidence: 82%

Section: Reactions Of [Zn(tu) 4 ](No 3 ) 2 With Dicarboxylatesmentioning

confidence: 99%

Backbone Flexibility and Counterion Effects on the Structure and Thermal Properties of Di(thiourea)zinc Dicarboxylate Coordination Polymers

et al. 2004

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“…The magic angle was adjusted first by minimizing the residual quadrupolar splitting in the rotor-synchronized 2 H MAS spectrum of a-oxalic acid [D 6 ]dehydrate. [12] The subsequent fine adjustment was carried out by maximizing the height of the ST 1 -CT shifted-echo signal in a one-dimensional STMAS experiment. [12,15] Static and MAS deuterium spectra were recorded with a Bruker 4 mm MAS probe.…”

Section: Methodsmentioning

confidence: 99%

“…[12] The subsequent fine adjustment was carried out by maximizing the height of the ST 1 -CT shifted-echo signal in a one-dimensional STMAS experiment. [12,15] Static and MAS deuterium spectra were recorded with a Bruker 4 mm MAS probe. A 500 W RF amplifier was used to give a 2 H 908 pulse duration of 2.9 ms.…”

Section: Methodsmentioning

confidence: 99%

A Synthetic Zwitterionic Water Channel: Characterization in the Solid State by X‐ray Crystallography and NMR Spectroscopy

et al. 2005

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Bio-inspired supramolecular frameworks are of both fundamental value as models and of practical importance in areas such as materials science, catalysis, and molecular electronics. [1][2][3] Many of these synthetic materials are constructed from metal ions as connectors and ligands as linkers, and are referred to as coordination polymers.[4] Porous materials are of particular interest, as the nanosized cavities lead to novel phenomena, with applications in separation, storage, and catalysis. In this respect, attempts to generate synthetic water channels that mimic aquaporin water channels [5] have met with some success. [6][7][8][9][10] Here we describe a zwitterionic, helical tube of nanodimensions that to some extent mimics aquaporin, and provide a detailed study of the water incorporated inside the channel over a wide temperature range by solidstate 2 H NMR spectroscopy. Reaction of the carboxy-functionalized imidazolium salt N,N'-diacetic acid imidazolium bromide [11] with zinc in aqueous solution affords zwitterionic coordination polymer 1 in crystalline form. The structure of 1 was characterized by single-crystal X-ray diffraction at 140 K and is shown in Figure 1. To ensure that the encapsulated water does not undergo any structural changes at ambient temperature, the structure was also determined at 293 K (see Supporting Information). The macrostructure is formed from ZnBr(H 2 O) units linked by bridging dicarboxylate anions, which assemble into helical channels and appear to be supported by weak pstacking interactions between the imidazolium moieties and by intrahelical hydrogen bonds. The strongest hydrogen bonds stem from contacts of the carboxy oxygen atom O2 to H3 and H6 in the next layer. Two molecules constitute a full cycle within the helix with distances between the layers of 6.234 . The cavity of the channel is occupied by water molecules, which form a one-dimensional chain with distances between the oxygen atoms of 3.157 .The coordination sphere around the zinc anion in 1 is best described as a distorted tetrahedron with angles between 92.5(2) and 117.1(1)8. Zinc-oxygen bond lengths lie between 1.997(2) and 2.014(3) , and both angles and bond lengths are in good agreement with those of comparable zinc dicarboxylate polymers. [12] The helices are packed in a hexagonal-based array with pronounced interhelical hydrogen bonding (Figure 2 b). Each asymmetric unit has five contacts shorter than 3 to neighboring helices, which arise from medium-strength interactions from O1 and O3 and weaker contacts from the bromide ligands. The hydrogen atoms H61 and H62 of the encapsulated water molecule are engaged in strong hydrogen

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“…Wiley-VCH ZAAC 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 6 There have been a number of studies reporting differences in families of materials based on phthalate, isophthalate, and terephthalate with second ligands [24][25][26][27][28][29], but none of these families display identical metal coordination environments regardless of the dicarboxylate isomer, as seen in 1-4. In most of these reports, dimensionality tends to increase from phthalate to isophthalate to terephthalate.…”

Section: Page 5 Of 18mentioning

confidence: 99%

Structural Trends in Coordination Polymers Containing Perfluorinated Dicarboxylates and 4,4′‐Bipyridine

Hulvey

Ayala

Cheetham

2009

Zeitschrift anorg allge chemie

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A new family of coordination polymers has been synthesized using cobalt or zinc, 4,4′‐bipyridine (4,4′‐bpy), and the perfluorinated dicarboxylates tetrafluoroterephthalate (tftpa), tetrafluorophthalate (tfpha), tetrafluoroisophthalate (tfipa), and tetrafluorosuccinate (tfsuc). These materials form under similar conditions and all display similar octahedral metal coordination environments despite significant differences in their structures. The compounds M(4,4′‐bpy)(tftpa)(H2O)2 (M = Co, Zn) (1) and M(4,4′‐bpy)(tfpha)(H2O)2 (M = Co, Zn) (2) are two‐dimensional layered structures, whereas Co(4,4′‐bpy)(tfsuc)(H2O)2 (3) and M(4,4′‐bpy)(tfipa)(H2O)2 (M = Co, Zn) (4) display three‐dimensional connectivity built up from two types of interconnected chains.

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Zinc dicarboxylate polymers and dimers: thiourea substitution as a tool in supramolecular synthesis

Cited by 36 publications

References 23 publications

Backbone Flexibility and Counterion Effects on the Structure and Thermal Properties of Di(thiourea)zinc Dicarboxylate Coordination Polymers

Backbone Flexibility and Counterion Effects on the Structure and Thermal Properties of Di(thiourea)zinc Dicarboxylate Coordination Polymers

A Synthetic Zwitterionic Water Channel: Characterization in the Solid State by X‐ray Crystallography and NMR Spectroscopy

Structural Trends in Coordination Polymers Containing Perfluorinated Dicarboxylates and 4,4′‐Bipyridine

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