Co-ordination engineering: when can one speak of an “understanding”? Case study of the multidentate ligand 2,2′-dimethyl-4,4′-bipyrimidine †

Janiak, Christoph; Uehlin, Lars; Wu, Heping; Klüfers, Peter; Piotrowski, Holger; Scharmann, Tobias G.

doi:10.1039/a904829d

Cited by 178 publications

(82 citation statements)

References 42 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…It is our experience that Ag(I) exhibits a marked tendency to adopt both chelating and monodentate donors with coordination frameworks when offered this possibility by a multimodal ligand (7,8). This coordination preference may be attributed to the drive of the system to adopt what may be termed a ''homogeneous'' metal coordination environment throughout the coordination polymer (9)(10)(11)(12). We now report the reaction of dpztz with Ag(I) and the structural characterization of a range of two-dimensional coordination frameworks with unusual network topologies and an unprecedented one-dimensional tubular ribbon constructed with metallacyclic units.…”

mentioning

confidence: 99%

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.

View full text Add to dashboard Cite

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...

show abstract

mentioning

confidence: 99%

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.

View full text Add to dashboard Cite

show abstract

“…The polyatomic counteranions play key roles in determining the molecular structures and behaviors since polyatomic anions have many characteristics such as negative charge, size, and geometry, and display variable differences, significant solvent effects, and pH dependence. [14][15][16][17][18] Recent developments in anion chemistry include exciting advances in anion template assembly, ion-pair recognition, the function of supramolecular materials, [19][20][21][22][23] environmental pollution, disease pathways, and biological processes.…”

mentioning

confidence: 99%

Anion Effects on Structure and Properties of Bis(3-methylimidazolium-1-yl) Salts

Noh¹,

Ahn

Na³

et al. 2011

Bulletin of the Korean Chemical Society

View full text Add to dashboard Cite

“…Recent and promising anion chemistry advances have been made in anion template assembly, ion-pair recognition, and anion functionality [17][18][19][20]. Some polyatomic anions in fact play crucial roles in the self-assembly of coordination materials, owing to attributes such as negative charge, a wide range of geometries, significant solvent effects, and pH dependence [21][22][23]. However, precise control of coordination geometry via (counter)anions remains a rare achievement, due to less effective electrostatic binding interactions.…”

Section: Introductionmentioning

confidence: 99%

Polyatomic anion versus acetonitrile in coordinating ability: structural properties of AgX-bearing 1,4-bis(2-isonicotinoyloxyethyl)piperazine (X− = NO3 −, CF3SO3 −, ClO4 −, BF4 −, and PF6 −)

Kim

Ahn

Kim

et al. 2011

Transition Met Chem

View full text Add to dashboard Cite

Type studies on competitive polyatomic anion versus acetonitrile coordination in the self-assembly of a series of [Ag 2 -, and PF 6 -; m = 0, 2; n = 0, 2, 4; bip = 1,4-bis(2-isonicotinoyloxyethyl)piperazine) were carried out. Each bip spacer acts as an N 4 tetradentate ligand and is linked to four silver(I) centers through two pyridine and two piperazine moieties, producing a double strand consisting of two 20-membered ring units. The coordinating environment around the silver(I) center is subtly determined by the competition of the polyatomic anions with acetonitrile, that is, by the AgÁÁÁNCCH 3 versus AgÁÁÁX interactions. The coordinating ability of acetonitrile is inversely proportional to the order of the coordination ability of the Hoffmeister series of polyatomic anions, NO 3 -) CF 3 SO 3 -[ ClO 4 -[ BF 4 -) PF 6 -.

show abstract

Co-ordination engineering: when can one speak of an “understanding”? Case study of the multidentate ligand 2,2′-dimethyl-4,4′-bipyrimidine †

Cited by 178 publications

References 42 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

Anion Effects on Structure and Properties of Bis(3-methylimidazolium-1-yl) Salts

Polyatomic anion versus acetonitrile in coordinating ability: structural properties of AgX-bearing 1,4-bis(2-isonicotinoyloxyethyl)piperazine (X− = NO3 −, CF3SO3 −, ClO4 −, BF4 −, and PF6 −)

Contact Info

Product

Resources

About