title: Self-assembly of the octanuclear cluster [Cu8(OH)10(NH2(CH2)2CH3)12]6+ and the one-dimensional N-propylcarbamate-linked coordination polymer {[Cu(O2CNH(CH2)2CH3)(NH2(CH2)2CH3)3](ClO4)}n.
abstract: The reaction of Cu(ClO4)2.6-H2O and n-propylamine in methanol gives two high-nuclearity products of well-defined compositions. At amine concentrations greater than seven equivalents compared to copper ion concentration, the system fixes carbon dioxide from air to form the one-dimensional carbamate-bridged coordination polymer, {[Cu(mu2-O,O'-O2CNH(CH2)2CH3)(NH2(CH2)2CH3)3](ClO4)}n ({1-ClO4}n). Lower relative amine concentrations lead to the self-assembly of an octanuclear copper-amine-hydroxide cluster [Cu8(OH)10(NH2(CH2)2CH3)12]6+ (2). Both compounds exhibit unique structures: {1-ClO4}n is the first mu2-O,O'-mono-N-alkylcarbamate-linked coordination polymer and 2 is the largest copper-hydroxide-monodentate amine cluster identified to date. The crystal structures indicate that the size of the n-propyl group is probably crucial for directing the formation of these compounds. Magnetic susceptibility studies indicate very weak antiferromagnetic coupling for 1. The octanuclear cluster 2 displays slightly stronger net antiferromagnetic coupling, despite the presence of a number of Cu-O(H)-Cu angles below the value of about 97 degrees that would normally be expected to yield ferromagnetic coupling.
authors.affiliation: University of Southern Denmark, Department of Chemistry, Campusvej 55, 5230 Odense M, Denmark.
authors.forename: Fabienne
authors.initials: F
authors.lastname: Bramsen
authors.forename: Andrew D
authors.initials: AD
authors.lastname: Bond
authors.forename: Christine J
authors.initials: CJ
authors.lastname: McKenzie
authors.forename: Rita G
authors.initials: RG
authors.lastname: Hazell
authors.forename: Boujemaa
authors.initials: B
authors.lastname: Moubaraki
authors.forename: Keith S
authors.initials: KS
authors.lastname: Murray