Field-dependent magnetic phenomena

The toluene solvates of meso-tetrakis(4-halophenyl)porphinatomanganese(III) tetracyanoethenide, [MnTFPP][TCNE] (1F), [MnTBrPP][TCNE] (1Br), and [MnTIPP][TCNE] (1I) have been prepared, and the magnetic and thermal properties have been determined and compared to those of [MnTClPP][TCNE] (1Cl). 1Br and 1I form uniform 1-D chains with each [TCNE](*)(-) being trans-m-N-sigma-bound to Mn(III) with Mn-N distances of 2.293 (1Br) and 2.276 (1I), which are a bit longer than 2.267 A observed for 1Cl. The Mn-N-C angles are 167.2, 168.1, and 158.7, while intrachain Mn.Mn separations are 10.189, 10.277, and 10.101 A. The magnetic susceptibilities for 1Br and 1I can be fit by the Curie-Weiss expression with high-temperature (T > 200 K) theta and low-temperature (T < 110 K) effective theta' values of -53 and 13 K and -79 and 30 K, respectively, compared to -60 and 13 K in 1Cl. theta is not observed for 1F; however, theta' is 70 K. The magnetic data are consistent with linear chain ferrimagnets composed of antiferromagnetically coupled S = 2 Mn(III) sites and S = (1)/(2) [TCNE](*)(-) sites with the antiferromagnetic intrachain coupling, J(intra/)k(B) (k(B) = Boltzmann's constant) determined from fits to the Seiden expression, of -225, -33, -30, and -53 K for the 1F, 1Cl, 1Br, and 1I, respectively. Hysteresis with coercive fields at 2 K of 20.0, 6.7, 4.0, and 15.9 kOe was observed for the 1F, 1Cl, 1Br, and 1I, respectively. Metamagnetic behavior is observed below 10 K for 1F, and below 5 K for both 1Br and 1I. The observed critical fields of 21.8, 6.8, 4.1, and 15.8 kOe were observed for 1F, 1Cl, 1Br, and 1I at 2 K, respectively. The ordering temperatures, T(c), determined from the maxima in the chi'(T) data taken at 10 Hz, are 28.0, 8.8, 8.0, and 6.5 K for 1F, 1Cl, 1Br, and 1I, respectively. The 28 K T(c) for 1F is the highest reported for this family of magnets.

Observation of Magnetic Ordering as High as 28 K for meso-Tetrakis(4-halophenyl)porphinatomanganese(III) Tetracyanoethenide, [MnTXPP][TCNE] (X = F, Br, I)

The metamagnetic behavior of the low temperature properties of single crystal Co(pyridine)2Cl2 is discussed. At 1.25 K oriented single crystals exhibit a two‐step metamagnetic transition at applied fields ∼0.8 and 1.6 kG along the b‐axis, a single transition at ∼0.7 kG for applied fields along the a* axis, and a single transition at ∼4.2 kG for an applied field along the c axis. Just above the transition fields a moment of 2μB/Co atom is measured for B0 parallel to the a* axis or b axis, and 0.4μB/Co atom is measured for the B0 parallel to the c axis. A large field dependent moment is observed at high fields. Many features of this compound closely mirror the behavior of CoCl2⋅2H2O. However, the Co(pyridine)2Cl2 has a much smaller interchain exchange, so that many features can be examined at lower fields. The basic features are consistent with a six‐sublattice model for the ordered antiferromagnetic system. Measurements of magnetic moment versus temperature show that Co(pyridine)2Cl2 does not obey a Curie–...

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Magnetic Properties of Linear Chain Systems: Metamagnetism of Single Crystal Co(pyridine) 2 Cl 2

The most authoritative reviews of exchange coupling in one-dimensional linear chain systems of transition-metal ions are now several years old.1–4 Recent advances are largely a result of systematic studies of magnetic properties in conjunction with structural determinations. Since a large number of systems have been investigated, we will discuss only one example of each type of behavior that has been found for each of the first-row transition-metal ions, and tabulate data for other systems which have figured prominently in the development of the field. For the most part, only those chain compounds for which rather complete structural and magnetic data are available will be considered here.

R. D. Spence

Papers

Metamagnetism of CoCl3[(CH3)3NH] · 2H2O