Abstract

Molecular silicon clusters with unsubstituted silicon vertices (siliconoids) have received attention as unsaturated silicon clusters and potential intermediates in the gas-phase deposition of elemental silicon. Investigation of behaviors of the siliconoids could contribute to the greater understanding of the transformation of silicon clusters as found in the chemical vapor deposition of elemental silicon. Herein we reported drastic transformation of a Si8R8 siliconoid to three novel silicon clusters under mild thermal conditions. Molecular structures of the obtained new clusters were determined by XRD analyses. Two clusters are siliconoids that have unsaturated silicon vertices adopting unusual geometries, and another one is a bis(disilene) which has two silicon–silicon double bonds interacted to each other through the central polyhedral silicon skeleton. The observed drastic transformation of silicon frameworks suggests that unsaturated molecular silicon clusters have a great potential to provide various molecular silicon clusters bearing unprecedented structures and properties.

Highlights

  • Molecular silicon clusters have attracted much attention as their characteristic electronic properties and reactivity depend on the structures [1,2,3,4,5]

  • In the chemical vapor deposition (CVD) process of elemental silicon, unsaturated silicon clusters with unsubstituted silicon vertices are considered as potential intermediates [6,7,8]

  • Such kinds of unsaturated molecular silicon clusters are synthesized as isolable molecules [9,10,11,12,13,14,15,16,17,18,19,20,21,22] and termed “siliconoids” by Scheschkewitz et al [10]

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Summary

Introduction

Molecular silicon clusters have attracted much attention as their characteristic electronic properties and reactivity depend on the structures [1,2,3,4,5]. In the chemical vapor deposition (CVD) process of elemental silicon, unsaturated silicon clusters with unsubstituted silicon vertices are considered as potential intermediates [6,7,8]. Such kinds of unsaturated molecular silicon clusters are synthesized as isolable molecules [9,10,11,12,13,14,15,16,17,18,19,20,21,22] and termed “siliconoids” by Scheschkewitz et al [10].

Thermal
Molecular
ORTEP drawing of ofof
Related silicon clusters and
Molecular Structure of 8
Molecular Structure of 9
Theoretical
General Procedures
Materials
Thermolysis of 4
Isolation of 7
Isolation of 8 and 9
X-ray Analysis
Theoretical Study
Conclusions
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