四芳基卟啉锰配离子的TCNQ电荷转移盐的合成和物理性质

合成了13个四芳基卟啉锰配离子的TCNQ电荷转移盐TAPMn]TCNQ]_n(TAPH₂=α,β,γ,δ-四芳基卟啉;A=C₆H₅,4-CH₃C₆H₄,4-CH₃OC₆H₄,4-ClC₆H₄,3-ClC₆H₄,3-FC₆H₄,4-(CH₃)₂NC₆H₄,2,4-Cl₂C₆H₃;TCNQ=7,7,8,8-四氰基对苯醌二甲烷;n=1,2).通过元素分析、IR、XPS、ESR、磁化率和电导率对其进行了表征.结果表明:这些电荷转移盐分子中存在TCNQ⁰和TCNQ^-,且TCNQ⁰和TCNQ^-之间存在相互作用,部分电荷从TCNQ]_n^-向TAPMn]⁺转移,导致化合物中的锰表现为混合价态.复合盐的室温电导率在10^-7～10^-10S·cm^-1,属于有机半导体,简单盐的室温电导率小于10^-11S·cm^-1.

Synthesis and Physical Properties of TCNQ Charge-transfer Salts of Tetraarylporphinatomanganese Complex Ions

Thirteen TCNQ charge transfer salts of tetraarylporphinatomanganese complex ions with the general formula TAPMn TCNQ n (TAPH 2=tetraarylporphyrin; A=C 6H 5, 4 CH 3C 6H 4, 4 CH 3OC 6H 4, 4 ClC 6H 4, 3 ClC 6H 4, 3 FC 6H 4, 2,4 Cl 2C 6H 3, 4 Me 2NC 6H 4; TCNQ =7,7,8,8 tetracyanoquinodimethane; n =1, 2) have been synthesized and characterized by elementary analyses, IR spectra, X ray photoelectron spectra, ESR spectra, magnetic susceptibilities and conductivities. The results indicate that there are TCNQ - and TCNQ 0 in the molecules of these charge transfer salts as well as interaction between TCNQ - and TCNQ 0. It leads manganese of these compounds to mixed valence state because partial electrons transfer from TCNQ - n to TAPMn +. The room temperature conductivities of the complex salts are between 10 -7 and 10 -10 S\5cm -1 , they belong to organic semiconductor. The conductivities of the simple salts are lower than 10 -11 S\5cm -1 .