In 1928 Heisenberg proposed [1] that bulk ferromagnetic order would only ever be achieved in systems containing heavy atoms, that is, metals, their oxides, and related derivatives. Indeed it was not until 1991 that the first organic ferromagnet was reported; the b-polymorph of the para-nitrophenyl nitronyl nitroxide radical (p-NPNN, 1; Scheme 1) was shown to order below 0.6 K. [2] Since then a number of other purely organic radicals have been found to undergo bulk ferromagnetic order, although the majority order below 1 K. Exceptions include the radical cation salts [C 60 ][TDAE] [3] (TDAE = tetrakis(dimethylamino)ethylene) and [BBDTA]-GaCl 4 [4](3; BBDTA = benzobis(1,3,2-dithiazolyl), which order as ferromagnets at 16 and 6.7 K, respectively. Of the neutral radicals, only the nitroxide-based diradical DOTM-DAA (2; DOTMDAA = N,N'-dioxy-1,3,5,7-tetramethyl-2,6diazaadamantane) orders ferromagnetically above 1 K (T c = 1.48 K), [5] although the dithiadiazolyl radical p-NCC 6 F 4 CNSSNC (4) orders as a weak ferromagnet at 36 K under ambient pressure, [6] the highest reported temperature for magnetic ordering in an organic radical. We have sought to prepare new dithiadiazolyl radicals, closely related to 4, in which small structural changes may lead to new magnetically ordered systems. Here we report the structure and magnetic properties of 5, which is only the second neutral organic radical to order as a ferromagnet above 1 K.

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The accurate structures of silsesquioxanes Si8O12H8 and Si8O12Me8 have been determined by gas-phase electron diffraction methods in order to obtain experimental data on single molecules unconstrained by a crystal lattice for comparison with data obtained by theoretical methods. For Si8O12H8 the experimentally determined structure shows ideal O h symmetry with Si−O distances and Si−O−Si angles of 161.41(3) pm and 147.9(2)° [r e, uncertainties (σ) in parentheses] compared with 162.9 pm and 147.8° for theoretical results from MP2/6-311++G(3df,3pd) calculations. In Si8O12Me8 a similar O h symmetry model gave experimental values of 161.74(5) pm and 148.9(2)° for the Si−O distances and Si−O−Si angles compared with calculated values of 163.2 pm and 148.6°, respectively.