A series of vanadogermanates from 1D chain to 3D framework built by Ge-V-O clusters and transition-metal-complex bridges.

Three novel extended vanadogermanates, {[(en)(2)Cd(2)Ge(8)V(12)O(40)(OH)(8)(H(2)O)]Cd(en)(2)}·6H(2)O (1), {[Zn(2)(dap)(3)]Zn(dap)Ge(6)V(15)O(48)(H(2)O)}Zn(dap)(2)(H(2)O)·3H(2)O (2), and {[Cd(3)(μ-dien)(2)(Hdien)(2)(H(2)O)(2)]Ge(4)V(16)O(42)(OH)(4)(H(2)O)}·2H(2)O (3; en=ethylenediamine, dap=1,2-diaminopropane, dien=diethylenetriamine), have been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectroscopy, powder XRD, thermogravimetric analysis, and single-crystal XRD. Their Ge-V-O cluster anions are derived from the V(18)O(42) cluster shell by replacing VO(5) square pyramids with Ge(2)O(7) groups. Compound 1 exhibits a 1D sinusoidal chain built up from rare inorganic-organic hybrid dicadmium-substituted vanadogermanate {Cd(en)V(12)O(40)(GeOH)(8)(H(2)O)} clusters and [Cd(en)(2)] complexes. Compound 2 is the first example of a 2D network based on linkage of the unusual {Ge(6)V(15)O(48)(H(2)O)} clusters and two types of Zn complex fragments. Compound 3 is an unprecedented 3D framework built by {Ge(4)V(16)O(42)(OH)(4)(H(2)O)} clusters and rare trinuclear bridging complex cations Cd(3)(μ-dien)(2)(Hdien)(2)(H(2)O)(2). Magnetic measurements illustrate that both 1 and 2 have antiferromagnetic exchange interactions between metal centers, whereas 3 exhibits ferrimagnetic behavior, which is rare in polyoxovanadate complexes.