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

• Published in: European Journal of Inorganic Chemistry Vol. 2009; no. 36; pp. 5550 - 5560
• Main Authors: Boyle, Timothy J., Tribby, Louis J., Ottley, Leigh Anna M., Han, Sang M.
• Format: Book Review Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 01.12.2009; WILEY‐VCH Verlag; Wiley
• Subjects: Alkoxides; Amides; Chemistry; Chemistry, Inorganic & Nuclear; Germanium; Nanomaterials; Physical Sciences; Science & Technology; Solid-state structures; Thiols; CORE-SHELL; BIVALENT GERMANIUM; Alkoxides; Thiols; MOLECULAR-STRUCTURE; NANOCRYSTALS; Nanomaterials; Amides; CRYSTAL-STRUCTURES; ALKOXIDE PRECURSORS; Solid-state structures; TIN(II) COMPOUNDS; STABLE GERMYLENES; Germanium; NANOWIRES; GE; crystal structure; amides; nanomaterials; thiols; alkoxides
• ISSN: 1434-1948; 1099-0682
• DOI: 10.1002/ejic.200900556

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(SiMe3)2]2 or [Ge(OtBu)2]2 and the appropriate ligand: N,N″‐dibenzylethylenediamine (H2‐DBED), tert‐butyl alcohol (H‐OtBu), 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(μc‐DBED)]2 (1, μc = bridging chelating), [Ge(μ‐DMP)(DMP)]2 (2), Ge(DPP)2 (3), [Ge(μ‐OtBu)(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 GeII 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 GeIV species 6 and 8. Using a simple solution precipitation methodology, Ge0 nanomaterials were isolated as dots and wires for the majority of precursors. Compound 7 led to the isolation of amorphous GexSy. 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) A series of GeII precursors―Ge[OC6H3(C6H5)2]2 shown―were synthesized for production of Ge0 nanomaterials. Upon precipitation from solution, it was found that Ge0 nanodots were formed from the amide, nanowires from alkoxides (shown) and siloxides, and amorphous GexSy from the silanthiolate.