CAJ | 학술논문

以氯化锰、双二苯基膦酸甲烷(dppm)及7,7,8,8-四氰基对醌二甲烷(TCNQ)为原料,合成了标题化合物[Mn(dppmdo)3][ (TCNQ)( DCBE)]1；利用X射线衍射、红外光谱、紫外-可见-近红外光谱和循环伏安等技术对合成产物进行了表征.结果表明,化合物1在近红外区发生配体TCNQ之间的电子转移(TCNQ/TCNQ-).化合物1中的TCNQ比游离态的TCNQ分子更容易被还原.室温下,化合物1的有效磁矩(12.7μB)远高于预期的由一个高自旋Mn2+离子(S=5/2)、一个TCNQ- (S=1/2)阴离子及一个DCBE-(S=1/2)阴离子组成基团的有效磁矩(4.58μB),表明它们之间存在着很强的磁相互作用.
이록화맹、쌍이분기련산갑완(dppm)급7,7,8,8-사청기대곤이갑완(TCNQ)위원료,합성료표제화합물[Mn(dppmdo)3][ (TCNQ)( DCBE)]1；이용X사선연사、홍외광보、자외-가견-근홍외광보화순배복안등기술대합성산물진행료표정.결과표명,화합물1재근홍외구발생배체TCNQ지간적전자전이(TCNQ/TCNQ-).화합물1중적TCNQ비유리태적TCNQ분자경용역피환원.실온하,화합물1적유효자구(12.7μB)원고우예기적유일개고자선Mn2+리자(S=5/2)、일개TCNQ- (S=1/2)음리자급일개DCBE-(S=1/2)음리자조성기단적유효자구(4.58μB),표명타문지간존재착흔강적자상호작용.
A new charge transfer compound,[ Mn(dppmdo) 3 ][ (TCNQ) (DCBE) ] 1 (dppmdo =bis(diphylphospine oxide) methane,DCBE =p-dicyanomethyl-benzoic methyl ester) was synthesized from the reaction of MnCl2·4H2O,bis(diphenylphosphino) methane (dppm),and 7,7,8,8-tetracyanoquinodimethane (TCNQ).As-synthesized product was characterized by means of X-ray crystallography,infrared spectrometry,ultraviolet-visible light-near infrared spectrometry,and cyclic voltammogram.Results indicate that compound 1 experiences low-energy transitions in near-infrared region,which can be attributed to the intra-ligand transitions involving radical anions (TCNQ/TCNQ-).Besides,TCNQ in 1 is easier to be reduced than free TCNQ molecule.And the effective magnetic moment of 1 at room temperature is as high as 12.7 μB,much larger than 4.58 μB,the expected effective magnetic moment of the radical consisting of one high spin Mn2+ ion (S =5/2),one TCNQ- (S =1/2) anion,and one DCBE-(S =1/2) anion,which indicates that there exist strong magnetic interactions among MnⅡcomplex ([Mn(dppmdo)3]2+),TCNQ- and DCBE- ions.