Journal
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
Volume -, Issue 19, Pages 3121-3131Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/ejic.201101292
Keywords
Copper; Coordination polymers; Single-strand molecular wheels; N; O ligands; Magnetic properties
Categories
Funding
- Greek State Scholarship Foundation (IKY)
- Royal Society of Chemistry Research Fund (UK)
- Spanish Centro de Investigacion Cientifica y Tecnologica (CICYT) [CTQ2009-07264]
- Catalan Institucio Catalana de Recerca i Estudis Avancats (ICREA)
- US National Science Foundation (NSF) [CHE-0910472]
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [910472] Funding Source: National Science Foundation
Ask authors/readers for more resources
The use of a-benzoin oxime (bzoxH2) in copper(II) benzoate chemistry, in the absence or presence of ancillary azido ligands, is reported. The reaction of Cu(O2CPh)2 center dot 2H2O with one equivalent of bzoxH2 in N,N-dimethylformamide (DMF) affords the decanuclear complex [Cu10(bzox)10(DMF)4] (1) in good yield. Dissolution of 1 in CH2Cl2 leads to the subsequent isolation of the solvent-free complex [Cu10(bzox)10] (2) in moderate yields. Complexes 1 and 2 are isostructural and possess a loop or single-strand molecular wheel topology. The bzox2 dianions behave as ?1:?1:?2:mu 3 ligands, which give rise to an overall [Cu10(mu-ONR)10(mu-OR')10] core. Both 1 and 2 stack to form nanotubular columns with beautiful supramolecular architectures. The reaction of Cu(O2CPh)2 center dot 2H2O with bzoxH2 and NaN3 in a 1:1:1 molar ratio in MeOH gives the bzoxH2-free complex [Cu(N3)(O2CPh)(MeOH)]n (3), which is a 1D chain. The CuII atoms in 3 are linked by a single, end-on N3 group, a syn,syn-?1:?1:mu PhCO2 ion, and an oxygen atom from the bridging MeOH ligand. The 1D chains are hydrogen bonded into 2D sheets through Nazide center dot H(OMeOH) interactions. Variable-temperature, solid-state direct-current magnetic studies were carried out on 13. The data for 1 and 2 indicate very strong antiferromagnetic exchange interactions and a S = 0 ground state, which is expected for even-membered loop arrays of CuII atoms. In contrast, 3 exhibits ferromagnetic exchange interactions; the data were fitted to the appropriate equation derived from the Hamiltonian H = JS(Si center dot Si+1), which includes a zJ' interchain interaction term. The best-fit parameters were J = +49.6(4) cm1, g = 2.067(3), and zJ' = 2.3(1) K. The combined results demonstrate the ligating flexibility of both the bzoxH2 and azido groups and their usefulness in the synthesis of polynuclear CuII clusters and coordination polymers.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available