Abstract
The treatment of excess zinc in the presence of ammonium chloride under ammonothermal conditions of 873 K and 97 MPa leads to diamminetriamidodizinc chloride [Zn2(NH3)2(NH2)3]Cl with a two-dimensionally μ-amido-interconnected substructure. Similar reaction conditions using ammonium bromide instead of the chloride (773 K, 230 MPa) result in diamminemonoamidozinc bromide [Zn(NH3)2(NH2)]Br with one-dimensional infinite μ-amido-bridged chains. Both compounds were obtained as colorless, very moisture sensitive crystals. Crystal structures and hydrogen bond schemes are analyzed. Raman spectroscopic data of the chloride are reported.
Highlights
Synthesis of high-quality nitride materials presents a challenge for various applications.In particular, semiconductor nitride materials are currently the focus of crystal growth, one example being GaN wafers as superior substrates for high-performance blue and white LEDs [1]
We have focused on the ammonothermal zinc nitride synthesis
We present the synthesis of [Zn2 (NH3 )2 (NH2 )3 ]Cl and [Zn(NH3 )2 (NH2 )]Br, two ammoniates of zinc halide amides, both with tetrahedral coordination by ammonia and amide ligands at the Zn central atom
Summary
Synthesis of high-quality nitride materials presents a challenge for various applications. Semiconductor nitride materials are currently the focus of crystal growth, one example being GaN wafers as superior substrates for high-performance blue and white LEDs [1]. A promising synthesis and crystal growth technique for such materials is the ammonothermal method, utilizing supercritical ammonia under either ammonoacidic or ammonobasic conditions. The technique may provide superior GaN crystals, but further interesting nitride materials. We have focused on the ammonothermal zinc nitride synthesis. In this respect, we have presented the ammonothermal synthesis and characterization of Zn(NH3 ) F2 and Zn(NH3 ) F2 , which show five-fold coordination at Zn [2]. The few further examples of ammoniates of zinc halides exclusively exhibit the tetrahedral environment of Zn, namely in [Zn(NH3 ) Cl2 ],
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