Diverse dimensionalities and structures in copper coordination polymers incorporating substituted aliphatic dicarboxylate ligands and 4,4 '-bipyridine

作者：Nettleman Joseph H; Szymanski Paul J; Sposato Laura K; LaDuca Robert L^*

来源：Inorganica Chimica Acta, 2010, 363(1): 225-233.

DOI：10.1016/j.ica.2009.08.031

• Copper
• Dicarboxylate
• Bipyridine
• Coordination polymer
• Thermogravimetric analysis
• Crystal structure
• Antiferromagnetism

Hydrothermal synthesis has afforded a series of divalent copper coordination polymers with substituted glutarate ligands and the rigid rod tether 4,4'-bipyridine (bpy): {[Cu(Hdmg)(2)(bpy)]center dot H(2)O}(n) (1, dmg = 3,3-dimethylglutarate), {[Cu(2)(dmg)(bpy)(2)](ClO(4))](n) (2), [Cu(2)(emg)(2)(bpy)](n) (3, emg = 3-ethyl, 3-methylglutarate) and [Cu(2)(cda)(2)(bpy)](n) (4, cda = 1,1-cyclopentanediacetate). All materials were characterized by single-crystal X-ray diffraction. Compound 1 manifests mu(2)-oxygen bridged [Cu(2)(Hdmg)(4)] "X"-patterns connected into a ribbon motif by bpy linkers. On the other hand, 2 possesses mixed-valence [Cu(I)Cu(II)Cu(II-)Cu(I)] tetrameric clusters bridged by dmg ligands and pillared into an 8-connected body-centered cubic (bcu) cationic lattice by bpy linkers. Compounds 3 and 4 are structurally very similar, displaying chain motifs with {Cu(2)(CO(2))(4)} paddlewheels connected by dicarboxylates, in turn conjoined into (4,4)-grid coordination polymer layers by bpy tethers. Variable temperature magnetic data indicate the presence of very strong antiferromagnetic coupling within the {Cu(2)(CO(2))(4)} paddlewheels in the latter two complexes, with g = 2.30(2) and J = -352(3) cm (1) for 3 and g = 2.35(2) and J = -352(5) cm (1) for 4. Significant structural contrasts are evident when compared to previously reported divalent copper/4,4'-bipyridine coordination polymers with unsubstituted or 2-methyl substituted glutarate ligands.

• 出版日期2010-1-4