Synthesis of Chlorine or Zinc Incorporated Indium Phosphide Magic Sized Cluster Families and Their Series of Multi-step Conversions

Abstract

InP magic sized clusters (MSCs) have attracted great interest to better understand the underlying mechanisms of InP quantum dot (QD) synthesis. InP MSCs that host heterogeneous atoms have not been properly studied so far. We report two families of InP MSCs that incorporate chlorine atoms (InP:Cl) or zinc atoms (InP:Zn). Methods to synthesize two InP:Cl MSCs (F360-InP:Cl MSCs; F399-InP:Cl MSCs) and three InP:Zn MSCs (F360-InP:Zn MSCs; F408-InP:Zn MSCs; F393-InP:Zn MSCs) were developed to obtain each directly from molecular precursors. Alternatively, each series of MSCs could be prepared by sequential conversions (Scheme 1). 386-InP MSCs ([In37P20](O2CR)51, R=alkyl) could be converted to F360-InP:Cl MSCs, then to F399-InP:Cl MSCs. Analogously, F360-InP:Zn MSCs could be converted to F408-InP:Zn MSCs, then to F393-InP:Zn MSCs. XRD, Raman, FT-IR, XPS, and NMR spectroscopies were performed to characterize the MSCs. Time-resolved spectroscopies revealed that 386-InP MSCs and F360-InP:Cl MSCs similarly behave like small molecules whereas F399-InP:Cl MSCs have QD-like characters. F360-InP:Zn MSCs was quite distinct from F408-InP:Zn MSCs and F393-InP:Zn MSCs, where the latter two MSCs shared the same inorganic skeleton and exhibited more QD-like characteristics. Studies on MSCs as QD intermediates can reveal unprecedented ways to rationally design nanostructures beyond conventional syntheses.