CePt3Si is a novel heavy fermion superconductor, crystallizing in the CePt3B structure as a tetragonally distorted low symmetry variant of the AuCu3 structure type. CePt3Si exhibits antiferromagnetic order at T(N) approximately 2.2 K and enters into a heavy fermion superconducting state at T(c) approximately 0.75 K. Large values of H(')(c2) approximately -8.5 T/K and H(c2)(0) approximately 5 T refer to heavy quasiparticles forming Cooper pairs. Hitherto, CePt3Si is the first heavy fermion superconductor without a center of symmetry.

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CeNiGe 3 , crystallizing in the orthorhombic SmNiGe 3 -type crystal structure, was studied by means of dc and ac magnetic susceptibility, magnetization, electrical resistivity, magnetoresistivity, Hall effect, and specific-heat measurements. The compound orders antiferromagnetically at T N ϭ5.5 K due to the presence of well localized 4 f magnetic moments, which are partly screened via a Kondo-like mechanism. The electrical behavior is governed by an interplay of Ruderman-Kittel-Kasuya-Yosida and Kondo interactions modified by crystal-field effects. The Kondo temperature is of similar magnitude as T N , and the overall crystal electric field splitting is of the order of 160 K. The low-temperature specific heat exhibits some enhancement indicating the formation of moderate-heavy quasiparticles in the antiferromagnetic state. The specific variation with applied magnetic field of the main physical characteristics of CeNiGe 3 points at a complex magnetic structure of the compound in the ordered region.

[micro-Tris(1,4-bis(tetrazol-1-yl)butane-N4,N4')iron(II)] bis(hexafluorophosphate), [Fe(btzb)(3)](PF(6))(2), crystallizes in a three-dimensional 3-fold interlocked structure featuring a sharp two-step spin-crossover behavior. The spin conversion takes place between 164 and 182 K showing a discontinuity at about T(1/2) = 174 K and a hysteresis of about 4 K between T(1/2) and the low-spin state. The spin transition has been independently followed by magnetic susceptibility measurements, (57)Fe-Mössbauer spectroscopy, and variable temperature far and midrange FTIR spectroscopy. The title compound crystallizes in the trigonal space group P3 (No. 147) with a unit cell content of one formula unit plus a small amount of disordered solvent. The lattice parameters were determined by X-ray diffraction at several temperatures between 100 and 300 K. Complete crystal structures were resolved for 9 of these temperatures between 100 (only low spin, LS) and 300 K (only high spin, HS), Z = 1 [Fe(btzb)(3)](PF(6))(2): 300 K (HS), a = 11.258(6) A, c = 8.948(6) A, V = 982.2(10) A(3); 100 K (LS), a = 10.989(3) A, c = 8.702(2) A, V = 910.1(4) A(3). The molecular structure consists of octahedral coordinated iron(II) centers bridged by six N4,N4' coordinating bis(tetrazole) ligands to form three 3-dimensional networks. Each of these three networks is symmetry related and interpenetrates each other within a unit cell to form the interlocked structure. The Fe-N bond lengths change between 1.993(1) A at 100 K in the LS state and 2.193(2) A at 300 K in the HS state. The nearest Fe separation is along the c-axis and identical with the lattice parameter c.

Combining experiments and ab initio models we report on SrPt4Ge12 and BaPt4Ge12 as members of a novel class of superconducting skutterudites, where Sr or Ba atoms stabilize a framework entirely formed by Ge atoms. Below T(c)=5.35 and 5.10 K for BaPt4Ge12 and SrPt4Ge12, respectively, electron-phonon coupled superconductivity emerges, ascribed to intrinsic features of the Pt-Ge framework, where Ge-p states dominate the electronic structure at the Fermi energy.

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We report on investigations of type I clathrate Si and Ge compounds with Ba partially substituted by rare earth atoms. Novel compounds from framework-deficient solid solutions Ba8 Alx Si42−3/4x □4−1/4x and Ba8 Gax Si42−3/4x □4−1/4x (x = 8, 12, 16; □, open square... lattice defect) have been prepared and characterized. All x-ray intensity data are consistent with the standardized clathrate I-Ba8Al16Ge30 type structure (space group Pm3̄n). In rare earth substituted clathrates, Eu2Ba6MxSi46−x (M = Cu, Al, Ga), rare earth atoms completely occupy the 2a position and thus form a new quaternary ordered version of the Ba8Al16Ge30 structure type. From a geometrical analysis of clathrate crystal structures, a systematic scheme for all known clathrate compounds is proposed. All clathrates studied are metals with low electrical conductivity. The highest Seebeck coefficient in the present series is deduced for Ba8In16Ge30, S = −75μV K−1, indicating transport processes dominated by electrons as carriers. The Eu-based clathrates investigated exhibit long-range magnetic order as high as 32 K for Eu2Ba6Al8Si36 of presumably ferromagnetic type. Magnetic susceptibility indicates in all cases a 2+ ground state for the Eu ions, in fine agreement with LIII absorption edge spectra.