Structures and Magnetic Properties of an Antiferromagnetically Coupled Polymeric Copper(II) Complex and Ferromagnetically Coupled Hexanuclear Nickel(II) Clusters
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资源简介：
Reactions between 2,6-diformyl-4-methylphenol (DFMF)
and tris(hydroxymethyl)
aminomethane (THMAM = H3L2) in the presence of copper(II)
salts, CuX2 (X = CH3CO2–, BF4–, ClO4–, Cl–, NO3–) and Ni(CH3CO2)2 or Ni(ClO4)2/NaC6H5CO2, sodium azide (NaN3), and triethylamine (TEA), in one pot self-assemble giving
a coordination polymer consisting of repeating pentanuclear copper(II)
clusters {[Cu2(H5L2–)(μ-N3)]2[Cu(N3)4]·2CH3OH}n (1) and hexanuclear
Ni(II) complexes [Ni6(H3L1–)2(HL22–)2(μ-N3)4(CH3CO2)2]·6C3H7NO·C2H5OH (2) and [Ni6(H3L1–)2(HL22–)2(μ-N3)4(C6H5CO2)2]·3C3H7NO·3H2O·CH3OH
(3). In 1, H5L2– and in 2 and 3 H3L1– and HL22– represent doubly deprotonated, singly
deprotonated, and doubly deprotonated Schiff-base ligands H7L and H4L1 and a tripodal ligand H3L2, respectively. 1 has a novel double-stranded ladder-like structure in which
[Cu(N3)4]2– anions link single
chains comprised of dinuclear cationic subunits [Cu2(H5L2–)(μ-N3)]+, forming a 3D structure of interconnected ladders through H bonding.
Nickel(II) clusters 2 and 3 have very similar
neutral hexanuclear cores in which six nickel(II) ions are bonded
to two H4L1, two H3L2, four μ-azido, and
two μ-CH3CO2–/μ-C6H5CO2– ligands. In
each structure two terminal dinickel (Ni2) units are connected
to the central dinickel unit through four doubly bridging end-on (EO)
μ-azido and four triply bridging μ3-methoxy
bridges organizing into hexanuclear units. In each terminal dinuclear
unit two nickel centers are bridged through one μ-phenolate
oxygen from H3L1–, one μ3-methoxy oxygen from HL22–, and one μ-CH3CO2– (2)/μ-C6H5CO2– (3) ion. Bulk magnetization measurements on 1 show moderately
strong antiferromagnetic coupling within the [Cu2] building
block (J1 = −113.5 cm–1). Bulk magnetization measurements on 2 and 3 demonstrate that the magnetic interactions are completely dominated
by ferromagnetic coupling occurring between Ni(II) ions for all bridges
with coupling constants (J1, J2, and J3) ranging from 2.10
to 14.56 cm–1 (in the Ĥ =
–J1(Ŝ1Ŝ2) – J1(Ŝ2Ŝ3) – J2(Ŝ3Ŝ4) – J1(Ŝ4Ŝ5) – J1(Ŝ5Ŝ6) – J2(Ŝ1Ŝ6) – J3(Ŝ2Ŝ6) – J3(Ŝ2Ŝ5) – J3(Ŝ3Ŝ5) convention).
创建时间：
2012-03-05
