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Synthesis and Theoretical Studies of a Double Helical Complex with the Ligand 4′,4′′′‐Bis(ferrocenyl)‐2,2′:6′,2′′:6′′,2′′′:6′′′,2′′′′‐quinquepyridine
Author(s) -
Aguado Javier E.,
Calhorda Maria José,
Costa Paulo J.,
Crespo Olga,
Félix Vitor,
Gimeno M. Concepción,
Jones Peter G.,
Laguna Antonio
Publication year - 2004
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200400057
Subject(s) - chemistry , supramolecular chemistry , trifluoromethanesulfonate , crystallography , stoichiometry , ferrocene , ligand (biochemistry) , pyridine , hydrogen bond , crystal structure , orthorhombic crystal system , stereochemistry , molecule , medicinal chemistry , electrochemistry , catalysis , organic chemistry , biochemistry , receptor , electrode
4′,4′′′‐Bis(ferrocenyl)‐2,2′:6′,2′′:6′′,2′′′:6′′′,2′′′′‐quinquepyridine (Fc 2 qpy) reacts with AgOTf (OTf = trifluoromethylsulfonate) to give a complex of stoichiometry [Ag(Fc2qpy)]OTf. The crystal structure reveals a dinuclear arrangement among the cations with an Ag ··· Ag close contact of 3.089(2) Å. The ligands are wrapped around the silver atoms in a double helical array. Further hydrogen bonding between triflate units and the protons of the ferrocene or pyridine moieties results in a supramolecular structure. Theoretical studies confirm the existence of a weak Ag−Ag bond, and show that the dinuclear form can be more stable than the mononuclear one, when there is a favorable balance between the reorganization energy of the two quinquepyridine chains and the energy released by the formation of stronger Ag−N bonds and the new Ag−Ag interaction in the helix. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)