Various transition-metal compound systems with intriguing characteristics have been investigated for the purpose of the comprehensive understanding of the crystal structures and the physical properties from macroscopic and microscopic viewpoints. For the vanadium oxides and polyanions, specifically Cu
xV
4O
11, Li
xV
3(P
2O
7)
3(PO
4)
2, Li
xV
2(PO
4)
3, Li
xVOPO
4, and LixVFPO4 that may be designed to serve as high-performance energy storage or thermoelectric device, the crystal structures, electronic properties, and spin dynamics are described on the basis of results of X-ray four-circle diffraction, electrical resistivity, thermoelectric power, magnetization, nuclear magnetic resonance, and electron paramagnetic resonance.
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