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1251324 
Journal Article 
Nanostructured magnetic cuprate cluster: synthesis, structure, UV-Vis spectroscopy, and magnetic properties of a new copper(II) arsenate NaCuAsO4 containing discrete [Cu4O16]24- clusters 
Ulutagay-Kartin, M; Hwu, SJ; Clayhold, JA 
2003 
Yes 
Inorganic Chemistry
ISSN: 0020-1669
EISSN: 1520-510X 
42 
7 
2405-2409 
English 
12665377 
WOS:000182029200036 
Crystals of copper(II) arsenate NaCuAsO(4) were grown by conventional high-temperature, solid-state methods in molten-salt media. The compounds were characterized by single crystal X-ray diffraction, UV-vis spectroscopy, and magnetic susceptibility measurements. NaCuAsO(4) crystallizes in a monoclinic lattice with a = 6.002 (1) A, b = 10.853 (2) A, c = 10.373 (2) A, beta = 91.50 (3) degrees, and V = 675.4(2) A(3); P2(1)/c (No. 14); Z = 8. The newly isolated sodium copper(II) arsenate reveals a pseudo-one-dimensional channel structure where the sodium cations reside. The extended framework contains nanostructured [Cu(4)O(16)](24-) magnetic clusters that are interlinked by closed-shell, nonmagnetic AsO(4)(3-) oxy anions via sharing vertex oxygen atoms of the CuO(5) and AsO(4) polyhedral units. Each [Cu(4)O(16)](24-) cluster consists of four CuO(5) square pyramidal units in a chair configuration centered by a center of inversion. The two crystallographically independent Cu(2+) cations adopt the [4 + 1] CuO(5) Jahn-Teller distortion giving rise to an intense d-d transition in UV-vis absorption spectra. The magnetic susceptibility measurements reveal that the title compound is antiferromagnetic. At high temperatures, the data follows a pure Curie law, suggesting noninteracting spins, but with a rapid suppression of the effective spin below T = 70 K. At low temperature, the susceptibility collapses, indicating spin gap formation as the magnetic-cluster material settles into the lowest energy magnetic singlet state. The current work in the exploratory synthesis of oxy compounds containing nanostructured transition-metal-oxide magnetic clusters leads to new materials for experimental and theoretical developments of magnetic models.