2,2′-Bi-1,6-naphthyridine metal complexes: a new ligand and a novel 2 × 2 inclined interpenetration of (4,4) nets or formation of helicoidal chains†

Wu, Heping; Janiak, Christoph; Uehlin, Lars; Klüfers, Peter; Mayer, Péter

doi:10.1039/a807522k

Cited by 78 publications

(32 citation statements)

References 12 publications

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“…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). Compound 4 is also the only structure reported here that does not adopt the ''Ag 2 (dpztz) 2 '' subunit within its structure.…”

Section: Comparison Of Structuresmentioning

confidence: 89%

“…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.…”

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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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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: 89%

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.

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“…[13] [57] for the ligandϪmetal packing notation for 5, 9؊12 is as in Scheme 4. has also been elucidated in the structures of the metal complexes with 2,2Ј-dimethyl-4,4Ј-bipyrimidine (2), [2] 5,5Ј-dicyano-2,2Ј-bipyridine (3), [3] and 2,2Ј-bi-1,6-naphthyridine (4). [4] These last three ligands also exhibit the sought for bridging and/or chelating bi-to tetradentate metal coordination. washed several times with water, dried and recrystallized from ethaemental analyzer E 240 C. Ϫ Commercial triphenylphosphane was nol to give 10 as colorless needles (yield 9.8 g, 64%).…”

Section: Infrared Spectroscopymentioning

confidence: 98%

“…[1] We have recently engaged into a program to study the coordination behavior of modified 2,2Ј-bipyridine ligands such as 2,2Ј-dimethyl-4,4Ј-bipyrimidine (2), [2] 5,5Ј-dicyano-2,2Ј-bipyridine (3), [3] 2,2Ј-bi-1,6-naphthyridine (4), [4] and modified tris(pyrazolyl)borate ligands. [5] As part of this program we report here the coordinating properties of ambidentate 5,5Ј-diamino-2,2Ј-bipyridine (5).…”

Section: Introductionmentioning

confidence: 99%

Modified Bipyridines: 5,5′-Diamino-2,2′-bipyridine Metal Complexes Assembled into Multidimensional Networks via Hydrogen Bonding and π–π Stacking Interactions

Janiak

Deblon

et al. 1999

Eur. J. Inorg. Chem.

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A new synthetic route for the synthesis of 5,5′‐diamino‐2,2‐bipyridine (5) based on the coupling of 2‐chloro‐5‐aminopyridine in the presence of NiCl2 × 6 H2O/PPh3/Zn in dimethylformamide is described. The reactions of the potentially ambidentate ligand 5 with salts of the transition metals Mn, Fe, Ni, Cu, Zn, Ag, and Cd gave a variety of 13 metal–ligand complexes depending on the anion, the crystallization conditions and the metal‐to‐ligand ratio. The complexes obtained were characterized by thermal analyses, NMR including 113Cd‐NMR, IR, and for the iron complex 57Fe‐Mößbauer spectroscopy. The structure of eight of the compounds was elucidated by X‐ray crystallography. All of these metal complexes show a bipyridine–metal coordination. The amino functionality was never involved in metal coordination. The intermolecular arrangement is dictated by hydrogen bonding from the amino functionality and by π–π stacking of the bipyridine rings.

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“…sein, in dem sich bei Katalysereaktionen sperrige Intermediate bilden, und die Stickstoffatome der Pyridinringe können möglicherweise als Koordinationsstellen bei Intercalationen dienen. [14] Diesen Ergebnissen zufolge ist zu vermuten, daû es eine groûe Gruppe von Metalloporphyrinatstrukturen gibt, deren Synthese allerdings noch aussteht. Einige Phasen mit ungewöhnlichen Porenöffnungen sollten durch Hydrothermalsynthese herstellbar sein.…”

Section: Experimentellesunclassified

SMTP-1: das erste funktionalisierte Metalloporphyrin-Molekularsieb mit großen Kanälen

Lin

1999

Angewandte Chemie

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Robuste hexagonale Hohlräume (Abmessungen 17×20×15 Å3), in die die Pyridylgruppen von cyclischen Metalloporphyrinhexameren hineinragen (siehe Bild), sind das charakteristische Strukturmotiv der nanoporösen Materialien [{M(tpyp)}6]⋅n G (M=Co, Mn; tpyp=Tetrakis(4‐pyridyl)porphyrinat; G=Gastmolekül), die aus MCl2 und H2tpyp hydrothermal hergestellt wurden. Das rhomboedrische Kristallgitter mit unendlichen hexagonalen Kanälen ist thermisch bis 400°C stabil, auch dann, wenn zuvor die Gastmoleküle entfernt wurden.

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2,2′-Bi-1,6-naphthyridine metal complexes: a new ligand and a novel 2 × 2 inclined interpenetration of (4,4) nets or formation of helicoidal chains†

Cited by 78 publications

References 12 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

Modified Bipyridines: 5,5′-Diamino-2,2′-bipyridine Metal Complexes Assembled into Multidimensional Networks via Hydrogen Bonding and π–π Stacking Interactions

SMTP-1: das erste funktionalisierte Metalloporphyrin-Molekularsieb mit großen Kanälen

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