Weak Effect on Tc with Increased Interchain Distances. Structure and Magnetic Properties of (meso-Tetrakis(3,5-di-tert-butyl-4-hydroxyphenyl)porphinato)manganese(III) Tetracyanoethenide, [MnIIITP‘P]+[TCNE]•-
- 1 January 1996
- journal article
- research article
- Published by American Chemical Society (ACS) in Inorganic Chemistry
- Vol. 35 (11) , 3083-3088
- https://doi.org/10.1021/ic9516267
Abstract
(meso-Tetrakis(3,5-di-tert-butyl-4-hydroxyphenyl)porphinato)manganese(III) tetracyanoethenide, [MnTP‘P][TCNE], has been structurally and magnetically characterized. [MnTP‘P][TCNE] (C96H108MnN8O4) belongs to the triclinic P1̄ (No. 2) space group with a = 8.597(2) Å, b = 14.756(4) Å, c = 17.573(5) Å, α = 101.16 (2)°, β = 100.56(2)°, γ = 96.37(2)°, and Z = 1. Due to the oxidative instability of the phenoxy groups, [MnIIITP‘P][TCNE] was prepared from the reaction of [MnIIITP‘P]OAc with the strong acid H2TCNE (pKa = 3.6) in the presence of TCNE to form acetic acid and the product. [MnTP‘P][TCNE] is a coordination polymer with the Mn(III) sites bridged by trans-μ2-bound [TCNE]•- with relatively short (8.587 Å) intrachain and long (≥14.756 Å) interchain Mn···Mn separations. The magnetic data above 210 K obey the Curie−Weiss expression with an effective ϑ value of 90.0 K, the largest yet reported for a soluble molecule-based magnet. In addition to a 15 K Tc hysteretic behavior with a coercive field of 100 Oe is observed at 5 K. Despite the significant steric bulk leading to the substantially decreased interchain interactions that are crucial for magnetic ordering, the Tc is unexpectedly high and suggests that other linear chain systems may be expected to exhibit magnetic ordering at higher temperatures.Keywords
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