Development of Superconducting Ferromagnet Based on New Verdazyl Radical Complex

近年来，有机铁磁体和超导体的发展受到了材料科学领域的广泛关注，并取得了很大的成功。另一方面，由于配合物的分子设计困难，超导态和反铁磁性或铁磁性有序共存于一个系统中的磁性超导体的例子非常有限。特别是由纯有机化合物组成的磁性超导体的例子尚未见报道。在本工作中，为了获得有机磁性导体，我们首先制备了几种磺酰基自由基阳离子的碘化盐(例如3-（4-和3-甲基吡啶）-1,5-二苯基磺酰基自由基（[p-MePyDV]^+和[m-MePyDV]^+）。这些碘化盐与Li^+[TCNQ]^-、Li^+[Me_2-TCNQ]^-和[n-Bu_4N]^+[Ni(dmit)_2]^-盐反应，得到与TCNQ、Me_2-TCNQ和Ni(dmit)_2阴离子组成的（1:1）的verdazyl阳离子盐。通过对（1:1）盐的氧化，制备了以TCNQ、Me_2-TCNQ和Ni(dmit)_2为阴离子的（1:2）和（1:3）绿dazyl阳离子盐。此外，还研究了这些自由基盐的磁性、电学性质和晶体结构。结果表明，这8种盐类是新型分子磁性半导体。

The development of organic ferromagnet and superconductor has attracted much attention in the field of material science, and many studies have been performed with great success in recent years. On the other hand, the examples of magnetic superconductors, where the superconducting state and antiferromagnetic or ferromagnetic order coexist in a system are very limited, because of the difficulty in molecular design of the complexes. Especially, the examples of the magnetic superconductor consisting of purely organic compounds have not been reported.In the present work, in order to obtain the organic magnetic conductors, first, we prepared several kinds of iodide salts of verdazyl radical cations (for example, 3-(4- and 3-methylpyridinium)-1,5-diphenylverdazyl radical cations ([p-MePyDV]^+ and [m-MePyDV]^+). These iodide salts were reacted with Li^+[TCNQ]^-, Li^+[Me_2-TCNQ]^-, and [n-Bu_4N]^+[Ni(dmit)_2]^- salts, giving the (1:1) salts of verdazyl cations with TCNQ, Me_2-TCNQ, and Ni(dmit)_2 anions. Several kinds of (1:2) and (1:3) salts of verdazyl cations with TCNQ, Me_2-TCNQ, and Ni(dmit)_2 anions were prepared by the oxidation of the (1:1) salts. Further, the magnetic and electric properties, and crystal structures of these radical salts have been studied. It has been clarified that the eight kinds of salts are new molecular magnetic semiconductors.