A Weakly Antiferromagnetically Coupled Biradical Combining Verdazyl with Nitronylnitroxide Units.

An antiferromagnetically (AFM) coupled biradical based on oxoverdazyl and nitronylnitroxide was synthesized in 46 % yield using Sonogashira coupling. The obtained heterobiradical evidenced distinct properties of both radical entities in solution. Depending on the solvent, the prepared biradical crystallized in two different forms. SQUID magnetization measurements on Form II showed coupling constants JintraII /kB =-2.1 K and zJinterII /kB =-11.5 K. Consequently, total intermolecular exchange interactions are five times larger than the intramolecular ones. Further, DFT calculations explained this phenomenon and indicated the advantage of Form I for further in-depth investigations.

Phase-sensitive dynamic susceptibility setup for measurements in pulsed magnetic fields.

Dynamic susceptibility, commonly referred to as AC susceptibility, χAC, is a powerful tool to characterize a material's magnetic properties in the presence of a magnetic field B, such as magnetic ordering or spin-relaxation phenomena. The standard technique for accessing χAC is based on measurements of the voltage which is induced in a coil by changes of a sample's magnetization in response to a small oscillating magnetic field. Importantly, this setup allows for a phase-sensitive detection of the susceptibility, thereby providing information on the magnetization dynamics. This method is frequently used in the low-field range, up to several Tesla, where DC fields are readily available. However, there is a growing demand for such magnetic measurements at higher fields, conveniently accessible by the use of pulse-field technology. Whereas various techniques are available for measuring the in-phase part of the susceptibility χAC ', none of them allows for the determination of the out-of-phase part χAC ″. Here we present a realization of an AC susceptometer for measurements of both the in- and out-of-phase component at frequencies up to 47 kHz and an oscillating amplitude of 1.5 mT in a pulsed magnetic field. With this setup, a magnetic signal of 3.6 × 10-6 emu can be resolved. As the setup also enables susceptibility measurements to be performed before and after the field pulse, it can be used to detect temperature changes in response to changes of the magnetic field. This will be demonstrated by measurements on the low-dimensional spin-1/2 system CuSO4·5H2O.

Planar Benzo[1,2- b:4,5- b']dithiophene Derivatives Decorated with Nitronyl and Imino Nitroxides.

Four weakly antiferromagnetic interacting biradicals of benzo[1,2- b:4,5- b']dithiophene (BDT) and BDT extended with two thiophenes (BDTTh2) linked with nitronyl and imino nitroxides (NN and IN) as BDT-NN, BDT-IN, BDTTh2-NN, and BDTTh2-IN were designed, synthesized, and characterized. Short intermolecular π-π distances were found (3.42 Å) for BDT-NN, whereas larger ones were found for BDT-IN (3.54 Å) and BDTTh2-NN (3.67 Å), respectively. Intramolecular magnetic interaction ( Jintra,exp/ kB) of BDT-NN (-26 K) is much larger than for BDT-IN (-5.3 K), while it is reduced for the dithiophene-extended molecule BDTTh2-NN (-2.3 K). Intermolecular interactions ( zJinter,exp/ kB) of BDT-NN (-6.5 K) and BDT-IN (-6.0 K) are stronger than for BDTTh2-NN (-4.6 K). Such large intermolecular couplings resulting from good π-stacking mark BDT-IN and BDTTh2-NN as promising crystalline materials with similar sized Jintra and Jinter. In addition, we also extracted a coupling within the chain of Jchain/ kB = -2.2 K and a coupling between the chains of zJinterchain = -1.5 K for BDTTh2-NN by a Heisenberg chain model. Intra- and intermolecular interactions and spin densities were examined by DFT studies.

Spin Frustration in an Organic Radical Ion Salt Based on a Kagome-Coupled Chain Structure.

Electro-oxidation of the quinoidal bisdithiazole BT in dichloroethane in the presence of [Bu4N][GaBr4] affords the 1:1 radical ion salt [BT][GaBr4], crystals of which belong to the trigonal space group P3. The packing pattern of the radical cations provides a rare example of an organic kagome basket structure, with S = 1/2 radical ion chains located at the triangular corners of a trihexagonal lattice. Magnetic measurements over a wide temperature range from 30 mK to 300 K suggest strongly frustrated AFM interactions on the scale of J/kb ∼ 30 K, but reveal no anomalies that would be associated with magnetic order. These observations are discussed in terms of the symmetry allowed magnetic interactions within and between the frustrated layers.