TY - JOUR
T1 - Synthesis of layered (2-D) V-based bimetallic oxalates from non-aqueous media that cannot be synthesized from aqueous media
AU - Min, Kil Sik
AU - Miller, Joel S.
PY - 2006
Y1 - 2006
N2 - The reaction of (NBu4)3[VIII(ox) 3] (1, ox = oxalate) and M(ii) (M = Fe, Co, Ni, Cu) ions in MeCN, leads to the isolation of V-based coordination polymers of [N(n-Bu) 4][FeIIVIII(ox)3]·0.30{[N(n- Bu)4](BF4)} (2), [N(n-Bu)4][Co IIVIII(ox)3]·0.75{[N(n-Bu) 4](BF4)} (3), [N(n-Bu)4][NiIIV III(ox)3]·0.20{[N(n-Bu)4](BF 4)}·0.20MeCN (4), and [N(n-Bu)4][Cu IIVIII(ox)2](BF4)2 (5) composition. Due to the lability of [VIII(ox)3] 3- to dissociate ox2-, these compounds cannot be prepared from aqueous media. 5 is best described as [N(n-Bu)4][V IIICuII(ox)2](BF4)2, and 2, 3, 4, and 5 are proposed to have a layered (2-D) motif for the M′M(ox)x (x = 2, 3) extended framework. The [V IIICuII(ox)2] composition of 5 is reported for the first time for a bimetallic oxalate. 2 shows a weak antiferromagnetic interaction between Fe(ii), S = 2 and V(iii), S = 1 ions ( = -9.4 K) within the 2-D layers. 3 and 5 do not magnetically order above 2 K. 4 magnetically order as ferromagnets below 2.55 K [taken as the onset of magnetization in χ″(T)], and has a glass transition temperature (χ′ max at 1000 Hz) at 2.26 K.
AB - The reaction of (NBu4)3[VIII(ox) 3] (1, ox = oxalate) and M(ii) (M = Fe, Co, Ni, Cu) ions in MeCN, leads to the isolation of V-based coordination polymers of [N(n-Bu) 4][FeIIVIII(ox)3]·0.30{[N(n- Bu)4](BF4)} (2), [N(n-Bu)4][Co IIVIII(ox)3]·0.75{[N(n-Bu) 4](BF4)} (3), [N(n-Bu)4][NiIIV III(ox)3]·0.20{[N(n-Bu)4](BF 4)}·0.20MeCN (4), and [N(n-Bu)4][Cu IIVIII(ox)2](BF4)2 (5) composition. Due to the lability of [VIII(ox)3] 3- to dissociate ox2-, these compounds cannot be prepared from aqueous media. 5 is best described as [N(n-Bu)4][V IIICuII(ox)2](BF4)2, and 2, 3, 4, and 5 are proposed to have a layered (2-D) motif for the M′M(ox)x (x = 2, 3) extended framework. The [V IIICuII(ox)2] composition of 5 is reported for the first time for a bimetallic oxalate. 2 shows a weak antiferromagnetic interaction between Fe(ii), S = 2 and V(iii), S = 1 ions ( = -9.4 K) within the 2-D layers. 3 and 5 do not magnetically order above 2 K. 4 magnetically order as ferromagnets below 2.55 K [taken as the onset of magnetization in χ″(T)], and has a glass transition temperature (χ′ max at 1000 Hz) at 2.26 K.
UR - http://www.scopus.com/inward/record.url?scp=33744921638&partnerID=8YFLogxK
U2 - 10.1039/b516198c
DO - 10.1039/b516198c
M3 - Article
AN - SCOPUS:33744921638
SN - 1477-9226
SP - 2463
EP - 2467
JO - Dalton Transactions
JF - Dalton Transactions
IS - 20
ER -