TY - JOUR
T1 - Magnetic anisotropy of CoII-WV ferromagnet
T2 - Single crystal and ab initio study
AU - Chorazy, Szymon
AU - Podgajny, Robert
AU - Majcher, Anna M.
AU - Nitek, Wojciech
AU - Rams, Michał
AU - Suturina, Elizaveta A.
AU - Ungur, Liviu
AU - Chibotaru, Liviu F.
AU - Sieklucka, Barbara
PY - 2013/4/7
Y1 - 2013/4/7
N2 - The novel layered {CoII3(2,2′-bpdo) 4(H2O)4[WV(CN)8] 2}·8H2O (1) network (2,2′-bpdo = 2,2′-bipyridine-1,1′-dioxide) is built of 2-D corrugated cyanide-bridged brick-wall skeletons parallel to the bc crystallographic plane. The coordination of chelating 2,2′-bpdo to Co(ii) gives 7-membered coordination rings. Magnetic and heat capacity measurements performed on monocrystalline samples reveal ferromagnetic ordering below TC of 6 K. Magnetic anisotropy of the ordered phase is represented by the easy axis oriented in the ac crystallographic plane. Bulk magnetic anisotropy is confronted with a local anisotropy of Co complexes: a strong axial anisotropy of trans,cis,cis-[CoII(μ-NC)2(H2O) 2(2,2′-bpdo)] moieties represented by gx (2) = 2.06, gy(2) = 2.95 and gz (2) = 7.30, and a planar anisotropy of trans,cis,cis-[Co II(μ-NC)2(2,2′-bpdo)2] represented by gx(3) = 5.40, gy(3) = 4.82 and gz(3) = 2.28, determined by CASSCF/RASSI/SINGLE-ANISO ab initio calculations. The experimental data are explained by the molecular field simulation of the magnetic structure using the above theoretical data.
AB - The novel layered {CoII3(2,2′-bpdo) 4(H2O)4[WV(CN)8] 2}·8H2O (1) network (2,2′-bpdo = 2,2′-bipyridine-1,1′-dioxide) is built of 2-D corrugated cyanide-bridged brick-wall skeletons parallel to the bc crystallographic plane. The coordination of chelating 2,2′-bpdo to Co(ii) gives 7-membered coordination rings. Magnetic and heat capacity measurements performed on monocrystalline samples reveal ferromagnetic ordering below TC of 6 K. Magnetic anisotropy of the ordered phase is represented by the easy axis oriented in the ac crystallographic plane. Bulk magnetic anisotropy is confronted with a local anisotropy of Co complexes: a strong axial anisotropy of trans,cis,cis-[CoII(μ-NC)2(H2O) 2(2,2′-bpdo)] moieties represented by gx (2) = 2.06, gy(2) = 2.95 and gz (2) = 7.30, and a planar anisotropy of trans,cis,cis-[Co II(μ-NC)2(2,2′-bpdo)2] represented by gx(3) = 5.40, gy(3) = 4.82 and gz(3) = 2.28, determined by CASSCF/RASSI/SINGLE-ANISO ab initio calculations. The experimental data are explained by the molecular field simulation of the magnetic structure using the above theoretical data.
UR - http://www.scopus.com/inward/record.url?scp=84874850436&partnerID=8YFLogxK
U2 - 10.1039/c2ce26387d
DO - 10.1039/c2ce26387d
M3 - Article
AN - SCOPUS:84874850436
SN - 1466-8033
VL - 15
SP - 2378
EP - 2385
JO - CrystEngComm
JF - CrystEngComm
IS - 13
ER -