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The impacts of Au-thiolate bonding on the near infrared (IR) luminescence of Au nanoclusters are studied by designing two types of monolayer reactions. Firstly, 1,4-dithiol durene (durene-DT) is reacted with Au(25) monolayer protected clusters (MPCs) stabilized by phenylethanethiolate (PhC2S) ligands. Upon the addition of durene-DT, the near IR luminescence of Au MPCs intensifies while the well-defined absorbance bands diminish. The optical transition is associated with the ligand exchange process monitored by proton NMR. In the second approach, PhC2S monothiols are reacted with durene-DT stabilized Au nanoclusters (DTCs). The addition of PhC2S to the Au DTCs induces the gradual decrease of the near IR luminescence. Mass spectrometry and NMR analysis reveal similar final products of mixed thiolate Au nanoclusters from both reactions. The results suggest that the 1,4-dithiolate-Au bonding interaction is a promising factor to further enhance the near IR luminescence of Au nanoclusters for biomedical applications.
Tang et al. (2012) studied this question.