The Versatile Chemistry and Noncentrosymmetric Crystal Structures of Salt-Inclusion Vanadate Hybrids


  • This work was supported by the National Science Foundation (NSF) (grant nos. DMR-0322905 and 0706426). Support from the NSF for the Summer Research Program in Solid State and Materials Chemistry (for R.P.; grant no. DMR-0303450), as well as the purchase of a SQUID magnetometer and an X-ray diffractometer, are also gratefully acknowledged. The authors are indebted to Prof. P. Shiv Halasyamani and Jaewook Baek of the University of Houston for their assistance in SHG measurements and to P.S.H. for invaluable discussions.


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Acentric vanadates: Three unique structure types of the vanadate-based mixed-metal oxide systems (salt)⋅MnII-VV-O and (salt)⋅CuII-VV-O are presented, with a focus on the role of the asymmetric vanadate units (yellow polyhedra). The two structure types found in the (AX)2M(VO3)2 series differ in the propagation direction of the metavanadate chains, which is thought to be due to the presence (or absence) of a Jahn–Teller distortion of the metal (d9 Cu2+ vs. d5 Mn2+) ion.