Synthesis and Characterization of Germanium Coordination Compounds for Production of Germanium Nanomaterials

A series of novel germanium(II) precursors was synthesized to initiate an investigation between the precursors' structures and the morphologies of the resulting nanoparticles. Theprecursors were synthesized from the reaction of Ge[N(SiMe 3 ) 2 ] 2 or [Ge(O t Bu) 2 ] 2 and the appropriate ligand: N , N ″‐dibenzylethylenediamine (H 2 ‐DBED), tert ‐butyl alcohol (H‐O t Bu), 2,6‐dimethylphenol (H‐DMP), 2,6‐diphenylphenol (H‐DPP), tert ‐butyldimethylsilanol (H‐DMBS), triphenylsilanol (H‐TPS), triphenylsilanethiol (H‐TPST), and benzenethiol (H‐PS). The products were identified as: [Ge(μ c ‐DBED)] 2 ( 1 , μ c = bridging chelating), [Ge(μ‐DMP)(DMP)] 2 ( 2 ), Ge(DPP) 2 ( 3 ), [Ge(μ‐O t Bu)(DMBS)] 2 , ( 4 ), [Ge(μ‐DMBS)(DMBS)] 2 ( 5 ), Ge(TPS) 3 (H) ( 6 ), [Ge(μ‐TPST)(TPST)] 2 ( 7 ), and Ge(PS) 4 ( 8 ). The Ge II metal centers were found to adopt a pyramidal geometry for 1 , 2 , 4 , 5 , 7 , a bent arrangement for 3 , and a tetrahedral coordination for the Ge IV species 6 and 8 . Using a simple solution precipitation methodology, Ge 0 nanomaterials were isolated as dots and wires for the majority of precursors. Compound 7 led to the isolation of amorphous Ge x S y . The nanomaterials isolated were characterized by TEM, EDS, and powder XRD. A correlation between the precursor's arrangement and final observed nanomorphology was proffered as part of the “precursor structure affect” phenomenon. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)