Reaction network governing diphosphine-protected gold nanocluster formation from nascent cationic platforms
Literature Information
John M. Pettibone, Jeffrey W. Hudgens
We identify the reaction network governing gold monolayer protected cluster (MPC) formation during the reduction of Au(PPh3)Cl and L5 (L5 = 1,5-bis(diphenylphosphino)pentane) in solutions. UV-vis spectroscopy and electrospray ionization mass spectrometry (ESI-MS) monitored the formation of ligated Aux: 6 ≤ x ≤ 12 clusters, which comprise the reaction intermediates and final products. Initially, predominantly [Au2L52]2+ complexes form through dissolution of Au(PPh3)Cl. These complexes control the reduction and nucleation reactions that form nascent phosphine-ligated Au8 and Au10 ionic clusters. [Au10L54]2+ is an observed growth platform for ligated Au11 and Au12 clusters. The data for syntheses of Au : L5 systems evidence that the nascent reaction products (t < 3 days) are less dependent on the chosen reducing agent (borane tert-butylamine complex or NaBH4); instead, after reduction ceases, subsequent solution phase processing provides greater control for tuning cluster nuclearity.
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