Formation of Artificial Receptors by Metal-Templated Self-Assembly

Linton, Brian R.; Hamilton, Andrew D.

doi:10.1021/cr960375w

Cited by 310 publications

(106 citation statements)

References 39 publications

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“…The modular selfassembly approach with defined rigid subunits allows for a rational design of discrete supramolecular entities (Fig. 1), while at the same time offering a wide variety of combinatorial assemblies based on a library of appropriate building blocks (17)(18)(19)(20)(21)(22)(23)(24). Thus, for example, combination of four tritopic 60°building blocks with six linear linkers gives rise to the formation of a tetrahedron whereas combination of the same 60°building blocks with a 109°angular linker gives rise to a trigonal bipyramid.…”

Section: Resultsmentioning

confidence: 99%

“…Besides the use of hydrogenbonded systems, the coordination-driven self-assembly of supramolecular species has become an important method (17)(18)(19)(20)(21)(22)(23)(24), because it allows for the incorporation of metal centers of various geometries and functionalities. Furthermore, the thermodynamic and kinetic stability of transition metal complexes can have a considerable advantage over pH-and temperaturesensitive biological systems.…”

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confidence: 99%

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Archimedean solids: Transition metal mediated rational self-assembly of supramolecular-truncated tetrahedra

Leininger

Fan

Schmitz

et al. 2000

Proc. Natl. Acad. Sci. U.S.A.

105

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Section: Resultsmentioning

confidence: 99%

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confidence: 99%

Archimedean solids: Transition metal mediated rational self-assembly of supramolecular-truncated tetrahedra

Leininger

Fan

Schmitz

et al. 2000

Proc. Natl. Acad. Sci. U.S.A.

105

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“…[2] The concept of metal-templated self-assembly in receptor design has been inspired by various biological systems in which proteins act as self-assembling binding sites. [3] Among the metalloproteins, zinc enzymes offer a large number of coordination motifs and thus provide models for the design of zinc-based anion receptors. [4] Our model for imidazole receptor design was the enzyme superoxide dismutase (SOD), which has a bimetallic Zn,Cu imidazole bridging moiety.…”

Section: Introductionmentioning

confidence: 99%

Development of Bis(2‐picolyl)amine–Zinc Chelates for Imidazole Receptors

Routasalo¹,

Helaja²,

Kavakka

et al. 2008

Eur J Org Chem

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New phenyl and phenol bis(2‐picolyl)amine (Dpa) derivatives have been synthesized in order to generate zinc chelates for imidazole anion receptors. Previously, binuclear phenolic zinc and copper chelates have shown affinity for pyrophosphate and guanidine anions, respectively. Herein we report significant imidazole affinity increasing from 2.38 × 106 to 2.90 × 107 for phenol‐bridged binuclear zinc–Dpa chelates, as evidenced by dynamic and titration 1H NMR studies. Among the Dpa chelates investigated, the zinc‐coordinated phenol group plays a crucial role in the mechanism of anion binding. Low‐temperature 1H NMR experiments suggest a σν‐symmetric geometry for the imidazole chelate. Computational DFT studies at the B3LYP level of theory imply that imidazole binding displaces the phenol bridge between the zinc ions.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

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“…A rtificial supramolecular hosts with stable and well defined structures formed by spontaneous self-assembly of molecular building blocks in organic solvents have shown great potential for inclusion phenomena, molecular recognition, or catalysis (1)(2)(3)(4)(5)(6)(7)(8)(9)(10)(11)(12). However, supramolecular complexes that operate in aqueous solution are rare (10)(11)(12)(13)(14).…”

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confidence: 99%

New supramolecular trigonal prisms from zinc(II)– 1,4,7,10-tetraazacyclododecane (cyclen) complexes and trithiocyanurate in aqueous solution

Aoki

Zulkefeli

Shiro

et al. 2002

Proc. Natl. Acad. Sci. U.S.A.

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The multiple bonding between multinuclear zinc(II)-1,4,7,10-tetraazacyclododecane (cyclen, a 12-membered tetraamine) complexes and multidentate ligands is an effective method for constructing supramolecular complexes having well defined and distinct structures in aqueous solution. Herein we present examples of supramolecular D 3h prisms formed by self-assembly of linearly dimeric or trimeric zinc(II)-cyclen complexes with a potentially trianionic C 3 subunit trithiocyanuric acid (TCA 3؊ ), wherein Zn 2؉ OS ؊ or Zn 2؉ ON ؊ coordination bonds and hydrogen bonds are responsible for stability of the multicomponent architectures in aqueous solution at neutral pH.A rtificial supramolecular hosts with stable and well defined structures formed by spontaneous self-assembly of molecular building blocks in organic solvents have shown great potential for inclusion phenomena, molecular recognition, or catalysis (1-12). However, supramolecular complexes that operate in aqueous solution are rare (10)(11)(12)(13)(14). While working on molecular recognition of imide functions by zinc(II) complexes of 12-membered tetraamine [Zn 2ϩ -1,4,7,10-tetraazacyclododecane (cyclen)] in aqueous solution (15-28), we tested interaction of cyanuric acid (CA) containing C 3 -symmetric three-imide functions with a C 3 -symmetric trinuclear zinc(II)-cyclen, Tris(Zn 2ϩ -cyclen) 1 [Zn 3 L 1 ; L 1 ϭ 1,3,5-Tris(1,4,7,10-tetraazacyclododecan-1-ylmethyl)benzene]. We have discovered quantitative formation of a 2:3 1-dianionic CA (CA 2Ϫ ) complex at neutral pH that is represented schematically as a trigonal prism 2 ( Fig. 1; ref. 29). More interestingly, we accidentally isolated a 4:4 assembly [(Zn 3 L 1 ) 4 -(CA 3Ϫ ) 4 ] from basic aqueous solution. The x-ray crystal structure showed four sets of completely deprotonated CA (CA 3Ϫ ) binding to three Zn 2ϩ -cyclen units from three different Zn 3 L 1 at each N Ϫ rim (29). Its outer shape may be viewed as a cuboctahedron 3a with 12 vertices occupied by Zn 2ϩ and its inner shell as a truncated tetrahedron 4a. It was unfortunate, however, to find that this 4:4 cuboctahedral complex collapsed in neutral H 2 O, possibly because of the extremely high pK a value of the third imide proton of CA. More recently (30), this problem was overcome by replacing CA for TCA, the thioimide functions of which possess lower pK a values [5.12 (pK 1 ), 8.24 (pK 2 ), and 11.69 (pK 3 )] than those of CA [6.85 (pK 1 ), 10.91 (pK 2 ), and Ͼ12 (pK 3 )]. As anticipated, TCA acted as a tridentate donor for three Zn 3 L 1 at neutral pH to yield a similar type of the 4:4 self-assembling supercomplex 3b, in which the deprotonated TCA 3Ϫ in an aromatic 1,3,5-triazine bound to 1 through Zn 2ϩ OS Ϫ (exocyclic) coordination bonds, and thus the 4:4 assembly is a chiral, twisted cuboctahedron. More interestingly, 3b [(Zn 3 L 1 ) 4 -(TCA 3Ϫ ) 4 ] encapsulates various sizematched and hydrophobic guest molecules such as adamantane in its inner cavity, which is represented as a twisted, truncated tetrahedron 4b. Thus, we discovered an approach to de...

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Formation of Artificial Receptors by Metal-Templated Self-Assembly

Cited by 310 publications

References 39 publications

Archimedean solids: Transition metal mediated rational self-assembly of supramolecular-truncated tetrahedra

Archimedean solids: Transition metal mediated rational self-assembly of supramolecular-truncated tetrahedra

Development of Bis(2‐picolyl)amine–Zinc Chelates for Imidazole Receptors

New supramolecular trigonal prisms from zinc(II)– 1,4,7,10-tetraazacyclododecane (cyclen) complexes and trithiocyanurate in aqueous solution

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