Charge-Transfer Effects in Ligand Exchange Reactions of Au25 Monolayer-Protected Clusters

Autor:	Royce W. Murray, Tessa M. Carducci, Raymond E. Blackwell
Rok vydání:	2015
Předmět:	Chemistry Ligand Nanoparticle Nanotechnology Benzeneselenol Electron chemistry.chemical_compound Crystallography Partial charge Reaction rate constant Monolayer Proton NMR General Materials Science Physical and Theoretical Chemistry
Zdroj:	The Journal of Physical Chemistry Letters. 6:1299-1302
ISSN:	1948-7185
Popis:	Reported here are second-order rate constants of associative ligand exchanges of Au25L18 nanoparticles (L = phenylethanethiolate) of various charge states, measured by proton nuclear magnetic resonance at room temperature and below. Differences in second-order rate constants (M(-1) s(-1)) of ligand exchange (positive clusters ∼1.9 × 10(-5) versus negative ones ∼1.2 × 10(-4)) show that electron depletion retards ligand exchange. The ordering of rate constants between the ligands benzeneselenol > 4-bromobenzene thiol > benzenethiol reveals that exchange is accelerated by higher acidity and/or electron donation capability of the incoming ligand. Together, these observations indicate that partial charge transfer occurs between the nanoparticle and ligand during the exchange and that this is a rate-determining effect in the process.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_dedup___::9058a319e7898aa5f695585479b6fdb5 https://doi.org/10.1021/acs.jpclett.5b00506 Zobrazit plný text záznamu