A New Macrobicyclic Tris‐bipyridine Ligand and Its Cu and Ag Complexes

Mendoza, Javier de; Mesa, Esther; Rodríguez‐Ubis, Juan Carlos; Vázquez, Purificación; Vögtle, Fritz; Windscheif, Paul-Michael; Rissanen, Kari; Lehn, Jean-Maríe; Lilienbaum, Daniel; Ziessel, Raymond

doi:10.1002/anie.199113311

Cited by 86 publications

(18 citation statements)

References 13 publications

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“…Firstly, Ag(I) is well known for its preference for a bis-bipyridyl coordination environment and this has been used widely as a design principle for the construction of discrete supramolecular species (36,37). There is only one previous report of the structural characterization of a Ag(I) cation sitting in a tris-bipyridyl environment (38). Secondly, as discussed in more detail above, when using multimodal ligands with Ag(I), we have observed a marked preference for the metal center to adopt a coordination environment with both chelating and monodentate ligands (7)(8)(9)(10)(11)(12).…”

Section: Comparison Of Structuresmentioning

confidence: 82%

Using multimodal ligands to influence network topology in silver(I) coordination polymers

Oxtoby

Blake

Champness

et al. 2002

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

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A range of Ag(I) one-and two-dimensional coordination frameworks has been prepared and structurally characterized by using the multimodal ligand 3,6-di-pyrazin-2-yl-(1,2,4,5)-tetrazine, which offers both monodentate and chelating binding sites. It is demonstrated that multimodal ligands can be used to prepare coordination frameworks with novel and unusual topologies and to influence the precise geometrical arrangement of both ligands and metal centers within such supramolecular arrays.crystal engineering ͉ supramolecular chemistry ͉ tetrazine T he synthesis of coordination frameworks represents an extremely topical area of research (1-3) that has developed dramatically over recent years with many advances in understanding the control of framework structure and topology. For example, the degree of interpenetration (4), polymeric dimensionality (5), and framework connectivity (6) can be controlled by the design of the constituent building blocks or crystallization conditions. We (7,8), among others (9-13), have been developing a strategy that uses multimodal bridging ligands that differ from more traditional tri-and tetradentate bridging systems in that they offer chemically distinct binding sites, both chelating and monodentate (Scheme 1). By using such ligands for coordination polymer construction, we aim to introduce further control over network formation by controlling the precise arrangement of metal centers with respect to each other and have recently reported examples of chiral Ag(I) coordination frameworks with diamondoid topology by using 2,2Ј-bipyrazine as the multimodal bridging ligand (7,8). We are also interested in the assembly of discrete supramolecular entities, metallacycles, or oligomeric supramolecular arrays into infinite coordination arrays (13). Our recent studies combining coordinatively flexible Cd(II) metal centers with the angular ligand 2,4Ј-(1,4-phenylene)bispyridine indicate that centrosymmetric metallacyclic units can be readily prepared by using simple ligand design (13). The latter study (13) also demonstrated that the metallacyclic units could be arranged into coordination frameworks by means of bridging of coordinated NO 3 Ϫ anions (13). We are now extending this work to use ligands that simultaneously encourage the formation of metallacyclic units and also intermetallacycle bridging.We have targeted 3,6-di-pyrazin-2-yl-(1,2,4,5)-tetrazine (dpztz), which has the potential to control the relative displacement of up to four coordinated metal centers in a zigzag fashion (Scheme 2). Although bis-2-pyridyl substituted 1,2,4,5-tetrazine units in principle allow coordination of two metal centers in cis-bidentate sites, in practice this coordination mode has never been observed and the trans-arrangement is always adopted (14-16). Dpztz also has the potential to form metallacyclic units with a suitably flexible transition metal, such as Ag(I), using both chelating and monodentate donors (Scheme 2e). It is our experience that Ag(I) exhibits a marked tendency to adopt both chelating and mono...

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Section: Comparison Of Structuresmentioning

confidence: 82%

Using multimodal ligands to influence network topology in silver(I) coordination polymers

Oxtoby

Blake

Champness

et al. 2002

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

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“…We now have a system which fulfills the prerequisites for a dynamic combinatorial library-two reactive aldehyde complexes in dynamic equilibrium with one another. Both 2,2 0bipyridine-5-carbaldehydes and 2,2 0 -bipyridine-5,5 0 -carbaldehydes 50 are known to react with tris(2-aminoethyl)amine (tren) to give open-chain (cap) or encapsulating ligands, respectively 73,79,80 and we planned to use this reaction to amplify the library of complexes.…”

Section: Amplification-selective Reaction and Interconversion Of Mer ...mentioning

confidence: 99%

Metal-directed assembly of combinatorial libraries—principles and establishment of equilibrated libraries with oligopyridine ligands

2007

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“…Moreover, we describe acid-catalysed processes of component exchange between different cages. As a preliminary step, a variety of structurally distinct dialdehydes ( A–H ; Scheme 1) have been reacted with the triamine “tren” (tris(2-aminoethyl)-amine; T ) to give hexaimine cages, extending the initial work on such processes 10–16,19. Following the dynamic covalent chemistry approach, dynamic libraries consisting of dialdehydes and triamine components were set up in order to analyse the self-sorting behaviour between the aldehydes employed.…”

Section: Introductionmentioning

confidence: 99%

Dynamic polyimine macrobicyclic cryptands – self-sorting with component selection

2019

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A New Macrobicyclic Tris‐bipyridine Ligand and Its Cu and Ag Complexes

Cited by 86 publications

References 13 publications

Using multimodal ligands to influence network topology in silver(I) coordination polymers

Using multimodal ligands to influence network topology in silver(I) coordination polymers

Metal-directed assembly of combinatorial libraries—principles and establishment of equilibrated libraries with oligopyridine ligands

Dynamic polyimine macrobicyclic cryptands – self-sorting with component selection

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