Preparations and Physical characterizations of the complexes of hexaaza macrocyclic metal cations with [Ni(S2C2(C6H5)2)2]- radical anion

• Main Authors: Huang, Chih-Ching, 黃志清
• Other Authors: Lee Lung-Si
• Format: Others
• Language: zh-TW
• Published: 1998
• Online Access: http://ndltd.ncl.edu.tw/handle/48122761214295906424

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.