| Summary: | 碩士 === 淡江大學 === 化學學系 === 86 === Macrocyclic metal complexes [NiCl2LR] ( LR=1,8-
disubstituted-1,3,6,8,10,13-hexaazacyclotetradecane ; R=C2H4OH ,
C2H5 , C3H6OH , C2H4CN , CH2C6H5, CH3 ) have been systhesized
and reacted with [Bu4N][Ni(dpt)2]( dpt =S2C2(C6H5)2 ) to form
various complexes of hexaaza macrocyclic metalcations with [Ni(
dpt)2]─radical anion. Four of the structures have been
determined by single-crystal X-ray diffraction analysis,
including[NiLR][Ni(dpt)2]*2CH3CN( R=C2H4OH 1 ; C2H5 2 ), [Bu4N]2
[NiLR]-[Ni(dpt)2]4( R=C3H6OH 3 ), [NiLR(CH3CN)2][Ni(dpt)2]2( R=
C2H4CN 4 ). [NiLR][Ni(dpt)2]2(R=CH2C6H5 5 ; CH3 6 ) have also
been prepared, but their structures havenot been determined.
Physical properties of the complexes, including ingrared
spectra, solution uv-visible spectra, and SQUID magnetic
susceptibilities have been measured. The infrared spectra
suggest that the[Ni(dpt)2] species in the complexes exist only
as monoanion. The crystalstructures show that molecular
geometries of the [Ni(dpt)2]─anions areessentially identical in
the four complexes The metal ions of the cationsare four-
coordinated with a nearly square-planar NiN4 environment in 1,
2,and 3, but is six-coordinated with a distorted octahedral NiN6
environmentin 4. The cations and anions are connected through
hydrogen bonds in 1 and2, however, are well-separated in 3 and
4. The magnetic susceptibilitymeasurements reveal that all the
complexes obey Curie-Wiss*s Law with smallnegative θvalues,
indicating weak antiferromagnetic interaction at low
temperatures. The antiferromagnetic interaction might result
from Ni***Scontacts between anions.
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