Crystal Engineering of Novel Materials Composed of Infinite Two- and Three-Dimensional Frameworks

Robson, Richard; Abrahams, Brendan F.; Batten, Stuart Robert; Gable, Robert W.; Hoskins, Bernard F.; Liu, Jianping

doi:10.1021/bk-1992-0499.ch019

Cited by 198 publications

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“…Thus, each Ag(I) center is linked to three others affording a twodimensional sheet structure that adopts a honeycomb arrangement or 6 3 net (Scheme 4c). No interdigitation between adjacent sheets is observed, and the voids within each sheet are occupied by the SbF 6 Ϫ counteranions. Such 6 3 net structures are well known in coordination frameworks where trigonal nodes, either metal centers or ligands, are linked by means of simple rods to afford the two-dimensional sheet arrangement.…”

Section: Resultsmentioning

confidence: 98%

“…Compounds 1-4 were prepared by reacting dpztz with the appropriate Ag(I)X salt (X ϭ PF 6 Ϫ , BF 4 Ϫ , SbF 6 Ϫ ) in MeCN in either a 2:1 (1) or 4:1 (2-4) Ag(I):dpztz ratio. The products were precipitated as dark pink microcrystalline solids by slow addition of diethyl ether.…”

Section: Resultsmentioning

confidence: 99%

“…The sheet is constructed such that chains of alternating Ag(I) centers and tetrazine rings run parallel to the a axis and Ag(I)-pyrazine chains run parallel to the b axis. The sheet is highly undulating, with a depth of about 13.0 Å, and adjacent sheets are interlocked (without any significant -interactions), allowing the formation of channels running parallel to the c axis that incorporate the PF 6 Ϫ counteranions. In contrast to {[Ag(dpztz)]PF 6 } ϱ , reaction of AgBF 4 with dpztz in a 4:1 ratio affords {[Ag 4 (dpztz) 3 (MeCN) 4 ](BF 4 ) 4 } ϱ 3.…”

Section: Resultsmentioning

confidence: 99%

“…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).…”

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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: Resultsmentioning

confidence: 98%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

mentioning

confidence: 99%

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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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“…[1] Trotz der vielversprechenden Aussicht, Festkörperstrukturen beeinflussen und vorhersagen zu können, [2] blühte das Kristall-Engineering erst im letzten Jahrzehnt auf. [3,4] Dabei entwickelte sich das Interesse nicht so sehr aus dem Wunsch heraus, Kristallstrukturen vorherzusagen, sondern vielmehr aus der Erkenntnis, daû die supramolekulare Synthese neuer Klassen funktionaler Festkörper eine natür-liche Konsequenz erfolgreichen Kristall-Engineerings ist.…”

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Von dissymmetrischen Molekülen zu chiralen Polymeren: ein neuer Impuls für die supramolekulare Synthese?

Zaworotko

1998

Angewandte Chemie

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Die ersten Früchte scheint ein neuer Zweig des Kristall‐Engineerings zu tragen: Ein nichtkovalent aufgebautes Netz, bestehend aus dem rechts als Stabmodell dargestellten Komplex, wurde direkt in ein Koordinationspolymer umgewandelt, dem eine ähnliche Grundstruktur zugrunde liegt. Die Tragweite dieser Arbeit reicht über die Grenzen der Koordinationschemie hinaus, da die Strategie auch auf organische und metallorganische Verbindungen anwendbar sein dürfte.

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Assembly of Chiral Two- and Three-dimensional Copper(I) Pseudohalide Based Coordination Polymers with Asymmetrically Substituted Pyrazine and Pyrimidine Ligands

Teichert

Sheldrick

1999

Z. anorg. allg. Chem.

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The coordination polymers ∞2[(CuCN)2(μ‐2 Mepyz)], ∞3[CuCN(μ‐2 Mepyz)] and ∞3[CuCN(μ‐4 Mepym)] (1–3) (2 Mepyz = 2‐methylpyrazine; 4 Mepym = 4‐methylpyrimidine) may be prepared by self‐assembly in acetonitrile solution at 100 °C (1, 3) or without solvent at 20 °C (2). All three contain ∞1[CuCN] chains that are bridged by the bidentate aromatic ligands into sheets in 1 and 3 D frameworks in 2 and 3. Reaction of CuSCN with these heterocyclic diazines at 100 °C leads to formation of the lamellar coordination polymers ∞2[(CuSCN)(μ‐2 Mepyz)] (4) and ∞2[CuSCN · (4 Mepym‐κN1)] (5), which contain respectively ∞1[CuSCN] chains and trans‐trans fused ∞2[CuSCN] sheets as substructures. The presence of an asymmetric substitution pattern in 2 Mepyz and 4 Mepym induces the adoption of a chiral structure by 2 and 5 (space groups P212121 and P1).

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Crystal Engineering of Novel Materials Composed of Infinite Two- and Three-Dimensional Frameworks

Cited by 198 publications

References 0 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

Von dissymmetrischen Molekülen zu chiralen Polymeren: ein neuer Impuls für die supramolekulare Synthese?

Assembly of Chiral Two- and Three-dimensional Copper(I) Pseudohalide Based Coordination Polymers with Asymmetrically Substituted Pyrazine and Pyrimidine Ligands

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