Silver(i) ions bridged by pyridazine: Doubling the ligand functionality for the design of unusual 3D coordination frameworks

Konstantin V. Domasevitch, Pavlo V. Solntsev, Il'Ya A. Gural'Skiy, Harald Krautscheid, Eduard B. Rusanov, Alexander N. Chernega, Judith A.K. Howard

Research output: Contribution to journalArticlepeer-review

101 Scopus citations


Nitrogen donor tetradentate ligands 4,4′-bipyridazine (bpdz) and pyridazino[4,5-d]pyridazine (pp) were prepared by inverse electron demand Diels-Alder cycloaddition reactions of 1,2,4,5-tetrazine. Examination of their behaviour towards silver(i) ions revealed a special potential of the ligands for the design of 3D coordination frameworks involving characteristic polynuclear and polymeric silver(i)-pyridazine motifs and multiple coordination of the ligands. Ag4(pp)5(ClO4)4 and Ag 4(pp)5(SiF6)(BF4) 2·4H2O adopt a unique 3D trinodal 4,4,5-connected topology based upon five-fold coordination of the metal ions and tetradentate bridging function of the organic modules. Complexes Ag3(L) 3(SO3CF3)3·nH2O and Ag4(L)3(X)4·nH2O (L = bpdz, pp; X = BF4-, 0.5SiF62-) illustrate formation of highly-connected frameworks incorporating trinuclear clusters as an origin of the net connectivity. In the carboxylate complexes Ag2(L)(RFCOO)2 (RF = CF3, C2F5, C3F7) the pyridazine and acido ligands act as complementary linkers for generation of 3D frameworks involving helicate motifs. Fused bicyclic pyridazine pp is a unique system combining very efficient σN-donor ability and pronounced π-acidity. The coordination frameworks commonly exhibit strong anion-π interactions, including unprecedented examples of double anion-π,π binding that occur between pyridazino[4,5-d]pyridazine as a double π,π-receptor for geometry complementary SiF62- anions.

Original languageEnglish (US)
Pages (from-to)3893-3905
Number of pages13
JournalDalton Transactions
Issue number35
StatePublished - 2007
Externally publishedYes


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