TY - JOUR
T1 - Synthesis, structure, and magnetic ordering of layered (2-D) V-based tris(oxalato)metalates
AU - Kil, Sik Min
AU - Rhinegold, Arnold L.
AU - Miller, Joel S.
PY - 2005/11/14
Y1 - 2005/11/14
N2 - The reaction of K3[MIII(ox)3] ·3H2O [M = V (1), Cr; ox = oxalate], Mn(II)/V(II), and [N(n-Bu)4]Br in water leads to the isolation of 2-D V-based coordination polymers, {[N(n-Bu)4][MnIIV III(ox)3]}n, (2), {[N(n-Bu)4][V IICrIII(ox)3]}n (3), {[N(n-Bu) 4][VIIVIII(ox)3]}n (4), and an intermediate in the formation of 4, {[N(n-Bu)4][V IIVIII(ox)3(H2O)2]} n·2.5H2O (4a), while 1-D [VII(ox)(H 2O)2]n (5) is obtained by using Na 2ox and [V(OH2)6]SO4 in water. The structures of 1-5 have been investigated by single crystal and/or powder X-ray crystallography. In 1, VIII is coordinated with three oxalate dianions as an approximately D3 symmetric, trigonally distorted octahedron. 1 is paramagnetic [μeff = 2.68 μB at 300 K, D = 3.84 cm-1 (D/kB = 5.53 K), θ = -1.11 K, and g = 1.895], indicating an S = 1 ground state. 2 exhibits intralayer ferromagnetic coupling below 20 K, but does not magnetically order above 2 K, and 3 shows a strong antiferromagnetic interaction between VII, S = 3/2 and CrIII, S = 3/2 ions (θ = -116 K) within the 2-D layers. 4 and 4a magnetically order as ferrimagnets at Tc's, taken as the onset of magnetization, of 11 and 30 K, respectively. The 2 K remanent magnetizations are 2440 and 2230 emu·Oe mol-1 and the coercive fields are 1460 and 4060 Oe for 4 and 4a, respectively. Both 4 and 4a clearly show frequency dependence, indicative of spin-glass-like behavior. The glass transition temperatures were at 6.3 and 27 K, respectively, for 4 and 4a. 1-D 5 exhibits antiferromagnetic coupling of -4.94 cm-1 (H = -2JΣi=1nSi·Si-1 gμBΣi=0nH·Si) between the VII ions.
AB - The reaction of K3[MIII(ox)3] ·3H2O [M = V (1), Cr; ox = oxalate], Mn(II)/V(II), and [N(n-Bu)4]Br in water leads to the isolation of 2-D V-based coordination polymers, {[N(n-Bu)4][MnIIV III(ox)3]}n, (2), {[N(n-Bu)4][V IICrIII(ox)3]}n (3), {[N(n-Bu) 4][VIIVIII(ox)3]}n (4), and an intermediate in the formation of 4, {[N(n-Bu)4][V IIVIII(ox)3(H2O)2]} n·2.5H2O (4a), while 1-D [VII(ox)(H 2O)2]n (5) is obtained by using Na 2ox and [V(OH2)6]SO4 in water. The structures of 1-5 have been investigated by single crystal and/or powder X-ray crystallography. In 1, VIII is coordinated with three oxalate dianions as an approximately D3 symmetric, trigonally distorted octahedron. 1 is paramagnetic [μeff = 2.68 μB at 300 K, D = 3.84 cm-1 (D/kB = 5.53 K), θ = -1.11 K, and g = 1.895], indicating an S = 1 ground state. 2 exhibits intralayer ferromagnetic coupling below 20 K, but does not magnetically order above 2 K, and 3 shows a strong antiferromagnetic interaction between VII, S = 3/2 and CrIII, S = 3/2 ions (θ = -116 K) within the 2-D layers. 4 and 4a magnetically order as ferrimagnets at Tc's, taken as the onset of magnetization, of 11 and 30 K, respectively. The 2 K remanent magnetizations are 2440 and 2230 emu·Oe mol-1 and the coercive fields are 1460 and 4060 Oe for 4 and 4a, respectively. Both 4 and 4a clearly show frequency dependence, indicative of spin-glass-like behavior. The glass transition temperatures were at 6.3 and 27 K, respectively, for 4 and 4a. 1-D 5 exhibits antiferromagnetic coupling of -4.94 cm-1 (H = -2JΣi=1nSi·Si-1 gμBΣi=0nH·Si) between the VII ions.
UR - http://www.scopus.com/inward/record.url?scp=28344448133&partnerID=8YFLogxK
U2 - 10.1021/ic051373+
DO - 10.1021/ic051373+
M3 - Article
AN - SCOPUS:28344448133
SN - 0020-1669
VL - 44
SP - 8433
EP - 8441
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 23
ER -