Heterodimetallic Compounds Assembled from Ferrocenedicarboxylato and Ferrocenecarboxylato Ligands
- 21 March 2003
- journal article
- Published by American Chemical Society (ACS) in Inorganic Chemistry
- Vol. 42 (8) , 2519-2530
- https://doi.org/10.1021/ic0205132
Abstract
Heteropolynuclear organometallic compounds have been constructed by using two kinds of ferrocene-based ligands, 1,1‘-ferrocenedicarboxylic acid (H2L1) and ferrocenecarboxylic acid (HL2). Reactions the ligand H2L1 with copper(II) and nickel(II) salts, in the presence of pyridine, give a tetranuclear Cu2Fe2 mixed-metallic box Cu2L12(Py)2(DMF)2(H2O)2 (1) and a tetranuclear heterobimetallic helix Ni2L12(Py)4(H2O) (2), respectively. In these complexes, the ferrocene moieties show cisoid conformations which lead to the formation of the finite coordination geometry, i.e. to molecular complexes. Interactions of the ligand H2L1 with lanthanide ions afford two-dimensional networks [La2L13(CH3OH)4]∞ (3), [Eu2L13(H2O)5]∞ (4), and [Gd2L13(CH3OH)2(H2O)3]∞ (5), respectively, in which transoid conformations of the ferrocene moiety provide opportunities to form infinite 2-D networks. It is suggested that the conformational freedom of the ferrocene moiety makes the ligand L1 display different conformations and coordination modes in these complexes. In addition, the π···π interactions related to the ferrocene moieties were also found to stabilize the supramolecular architectures in the solid state. As a comparison, reaction of lanthanide ions with the ligand HL2 resulted in three isostructural heterodinuclear windmill-shaped compounds Ln2L26(CH3OH)2(H2O)5 [Ln = La (6), Eu (7), and Gd (8)] by simply diffusing the solutions of lanthanide ions into the mixture of HL2 and NaOH, respectively. Electrochemical properties of the ferrocene-containing complexes 1 − 8 are also investigated in the solution or solid state.Keywords
This publication has 100 references indexed in Scilit:
- Syntheses, Structures, and Magnetic Properties of Two Gadolinium(III)–Copper(II) Coordination Polymers by a Hydrothermal ReactionPublished by Wiley ,2000
- Hang-gliding with Ferrocenes: Unusual Coordination Chemistry of 1,1‘-Bis(mesitylthio)ferroceneOrganometallics, 2000
- Design Strategies for Solid-State Supramolecular Arrays Containing Both Mixed-Metalated and Freebase PorphyrinsJournal of the American Chemical Society, 1999
- Crystal supramolecular motifs. Two- and three-dimensional networks of Ph4P+ cations engaged in sixfold phenyl embracesJ. Chem. Soc., Dalton Trans., 1998
- Diversity of linking modes by N,N′-p-phenylenedimethylenebis(pyridin-4 -one) [p-XBP4] in the novel ‘linked lantern’ framework complex {[Nd2(p-XBP4)6(H2O)4 ](p-XBP4)(H2O)3(ClO4) 6}nChemical Communications, 1997
- A self-assembled macrocyclic tetranuclear molecular square [Co(HL)]44+ [H2L = tetra(2-pyridyl)thiocarbazone]Chemical Communications, 1997
- Dinuclear Catecholate Helicates: Their Inversion MechanismJournal of the American Chemical Society, 1996
- Structure of the [1.1]metallocenophanes of iron and ruthenium. Single-crystal x-ray diffraction analysis of (C5H4-CH2-C5H4)2Fe2, (C5H4-CH2-C5H4)2FeRu, and (C5H4-CH2-C5H4)2Ru2Organometallics, 1992
- Polarographic and magnetic susceptibility study of various biferrocene compoundsInorganic Chemistry, 1973
- Organic Chemistry of Ferrocene. II. The Preparation of Ferrocenyl AliphaticJournal of the American Chemical Society, 1957