Homo‐ and Heterometallic Coordination Oligomers and Polymers Derived from the Preformed Complexes [Cu(bdmpp)(MeCN)2](ClO4)2, [Cu(bdmpp)(N3)2], and [Cu(bdmpp)(N3)(μ‐N3)]2 [bdmpp = 2,6‐bis(3,5‐dimethyl‐1H‐pyrazol‐1‐yl)pyridine]: Syntheses, Structures, and Redox Properties

Abstract

AbstractReactions of three CuII complexes of 2,6‐bis(3,5‐dimethyl‐1H‐pyrazol‐1‐yl)pyridine (bdmpp), [Cu(bdmpp)(MeCN)2](ClO4)2 (1), [Cu(bdmpp)(N3)2]·1.5H2O (2·1.5H2O), and [Cu(bdmpp)(N3)(μ‐N3)]2·2MeOH (3·2MeOH), with 4,4′‐bipy, dicyanamide (dca), azide, and MCl2 (M = Cu, Co, Ni) yield a series of homo‐ and heterometallic coordination oligomers and polymers, [{Cu(bdmpp)(ClO4)}2(μ‐4,4′‐bipy)](ClO4)2 (4), {[Cu(bdmpp)(μ‐dca)](ClO4)}n (5), {[Cu(bdmpp)(μ‐N3)](ClO4)·MeCN}n (6), [{Cu(N3)(bdmpp)}2(μ‐N3)2Cu(N3)2] (7), and [{Cu(μ‐N3)(bdmpp)(μ‐N3)M(μ‐N3)(X)}2·eMeCN]n (8: M = Co, X = N3, e = 0; 9: M = Ni, X = Cl; e = 4). Compounds 1–9 have been characterized by elemental analysis, IR spectroscopy, and single‐crystal X‐ray crystallography. Compound 4 has a centrosymmetric dimeric dication structure in which two [Cu(bdmpp)(ClO4)]+ fragments are bridged by one 4,4′‐bipy. Compounds 5 and 6 have a 1D linear or spiral chain extending along the b axis in which each [Cu(bdmpp)]2+ fragment is linked through bridging dca or azide anions, respectively. Compound 7 has a trinuclear sandwich structure in which two molecules of 2 link a Cu(N3)2 species through two end‐on bridging azide anions. Compounds 8 and 9 have a similar 1D chain structure extending along the c axis in which [Cu(μ‐N3)(bdmpp)(μ‐N3)M(μ‐N3)(X)]2 (M = Co, Ni) molecules are linked by end‐to‐end azide anions (8) or end‐on azide anions (9). In addition, the electrochemical properties of 1–9 in DMF were investigated by cyclic voltammetry. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)