摘要
The structure [MnmTPP][Me2DCNQI] （TPP = tetraphenylporphinato; Me2DCNQI = 2,5-dimethyl-N,N＇-dicyanoquinonediimine） has been determined from X-ray powder diffraction data. The nonsolvated structure is composed of linear （I-D） chains of alternating [MnmTPP]＋ and ta-[MezDCNQI]＇- with intrachain Mn...Mn separations of 12.83 A, and a Mn-NDcNQI distance of 2.18A. The dihedral angle between the mean Mn（N4）xpp and [MezDCNQI]＇-planes, and the Mn-（N-C）ocNQ1 angle are 84.18° and 143.6°, respectively. [MnInTpP][MezDCNQI] has a Tc of 4.3 K from the 10 Hz x（T） data, 2-K coercivity of 5,600 Oe, and 6,300 emuOe/mol remnant magnetization that are reduced from that observed for related materials, and their in- clusion extends the magnetostructural correlation between the intrachain coupling and both the dihedral angle between the mean Mn（N4）xPp and [TCNE]＇-（TCNE --- tetracyanoethylene） planes and Mn-（N-C）Tcr angles. This is in accord with the in- trachain coupling arising from the overlap of the Mnm dz2-1ike singly occupied molecular orbital （SOMO） and the z component of the [TCNE]- π＊ （π2＊） SOMO, which increases with decreasing dihedral angle between the mean Mn（N4）xep and [TCNE]＇- planes and Mn-（N-C）TcNE angle.
The structure [MnⅢ TPP][Me2 DCNQI] (TPP = tetraphenylporphinato; Me 2 DCNQI = 2,5-dimethyl-N,N′-dicyanoquinonediimine) has been determined from X-ray powder diffraction data. The nonsolvated structure is composed of linear (1-D) chains of alternating [MnⅢ TPP] + and μ-[Me 2 DCNQI] with intrachain Mn···Mn separations of 12.83 , and a Mn N DCNQI distance of 2.18. The dihedral angle between the mean Mn(N 4 ) TPP and [Me 2 DCNQI].- planes, and the Mn (N C) DCNQI angle are 84.18° and 143.6°, respectively. [MnⅢ TPP][Me 2 DCNQI] has a T c of 4.3 K from the 10 Hz χ"(T) data, 2-K coercivity of 5,600 Oe, and 6,300 emuOe/mol remnant magnetization that are reduced from that observed for related materials, and their inclusion extends the magnetostructural correlation between the intrachain coupling and both the dihedral angle between the mean Mn(N 4 ) TPP and [TCNE]*- (TCNE = tetracyanoethylene) planes and Mn (N C) TCNE angles. This is in accord with the intrachain coupling arising from the overlap of the MnⅢ d z 2 -like singly occupied molecular orbital (SOMO) and the z component of the [TCNE]*-π* (πz *) SOMO, which increases with decreasing dihedral angle between the mean Mn(N 4 ) TPP and [TCNE]*- planes and Mn (N C) TCNE angle.
基金
The structure reported in this paper has been deposited with the Cambridge Crystallographic Data Center as Supplementary Publication CCDC No.870451
