title: Supramolecular functionalization and concomitant enhancement in properties of Au(25) clusters.
abstract: We present a versatile approach for tuning the surface functionality of an atomically precise 25 atom gold cluster using specific host-guest interactions between β-cyclodextrin (CD) and the ligand anchored on the cluster. The supramolecular interaction between the Au25 cluster protected by 4-(t-butyl)benzyl mercaptan, labeled Au25SBB18, and CD yielding Au25SBB18∩CDn (n = 1, 2, 3, and 4) has been probed experimentally using various spectroscopic techniques and was further analyzed by density functional theory calculations and molecular modeling. The viability of our method in modifying the properties of differently functionalized Au25 clusters is demonstrated. Besides modifying their optoelectronic properties, the CD moieties present on the cluster surface provide enhanced stability and optical responses which are crucial in view of the potential applications of these systems. Here, the CD molecules act as an umbrella which protects the fragile cluster core from the direct interaction with many destabilizing agents such as metal ions, ligands, and so on. Apart from the inherent biocompatibility of the CD-protected Au clusters, additional capabilities acquired by the supramolecular functionalization make such modified clusters preferred materials for applications, including those in biology.
authors: DST Unit of Nanoscience (DST UNS) and Thematic Unit of Excellence, Department of Chemistry, Indian Institute of Technology Madras , Chennai 600036, India.
authors: Ammu
authors: A
authors: Mathew
authors: Ganapati
authors: G
authors: Natarajan
authors: Lauri
authors: L
authors: Lehtovaara
authors: Hannu
authors: H
authors: Häkkinen
authors: Ravva Mahesh
authors: RM
authors: Kumar
authors: Venkatesan
authors: V
authors: Subramanian
authors: Abdul
authors: A
authors: Jaleel
authors: Thalappil
authors: T
authors: Pradeep
mesh_terms: D006046:Gold / Q000737:chemistry*; D015335:Molecular Probes; D019032:Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization; D013056:Spectrophotometry, Ultraviolet
chemical_list: D015335:Molecular Probes; D006046:Gold