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Self‐Assembly of the Octanuclear Cluster [Cu 8 (OH) 10 (NH 2 (CH 2 ) 2 CH 3 ) 12 ] 6+ and the One‐Dimensional N ‐Propylcarbamate‐Linked Coordination Polymer {[Cu(O 2 CNH(CH 2 ) 2 CH 3 )(NH 2 (CH 2 ) 2 CH 3 ) 3 ](ClO 4 )} n
Author(s) -
Bramsen Fabienne,
Bond Andrew D.,
McKenzie Christine J.,
Hazell Rita G.,
Moubaraki Boujemaa,
Murray Keith S.
Publication year - 2005
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200400555
Subject(s) - chemistry , copper , amine gas treating , crystallography , antiferromagnetism , hydroxide , denticity , crystal structure , cluster (spacecraft) , inorganic chemistry , propylamine , organic chemistry , physics , computer science , programming language , condensed matter physics
The reaction of Cu(ClO 4 ) 2 ⋅6 H 2 O 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(μ 2 ‐ O , O′ ‐O 2 CNH(CH 2 ) 2 CH 3 )(NH 2 (CH 2 ) 2 CH 3 ) 3 ](ClO 4 )} n ({ 1 ‐ClO 4 } n ). Lower relative amine concentrations lead to the self‐assembly of an octanuclear copper‐amine‐hydroxide cluster [Cu 8 (OH) 10 (NH 2 (CH 2 ) 2 CH 3 ) 12 ] 6+ ( 2 ). Both compounds exhibit unique structures: { 1 ‐ClO 4 } n is the first μ 2 ‐ 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° that would normally be expected to yield ferromagnetic coupling.