Postsynthetic modification of gold nanoparticles with calix[4]arene enantiomers: origin of chiral surface plasmon resonance.

Gold nanoparticles postsynthetically modified with chiral 1,3-disubstituted diamino calix[4]arene ligands 2a and 2b are shown to exhibit a circular dichroism (CD)-active surface plasmon resonance absorption (SPR) band. Electronic communication between adsorbed ligand and the gold nanoparticle surface is evidenced in an almost 10-fold increase in the ligand molar ellipticity in the pi-pi* transition spectral range when bound to the gold surface relative to free solution. The footprint of ligand on the gold nanoparticle surface at saturation is measured to be 91 A(2) via monitoring the red shift in the SPR band accompanying ligand adsorption. At ligand concentrations above that required for surface saturation, the ellipticity of the band in the SPR spectral range plateaus to a constant value, whereas the ellipticity of the band in the pi-pi* transition spectral range continues to increase in a manner that corresponds to free ligand in solution. This critical observation correlates ligand adsorption and the onset of the CD-active SPR band. On the basis of the packing characteristics of the bulky calixarene ligand, which are controlled by achiral tert-butyl groups, and the postsynthetic nature of nanoaprticle surface modification of 4.7 nm gold cores used in this study, which precludes synthesis of chiral arrangements of gold atoms, a mechanism responsible for the CD-active SPR bands is proposed, which is based upon the influence of the asymmetric center of the chiral adsorbate on the electronic states of the metal nanoparticle core-an explanation supported by the observed interactions between the gold surface and adsorbed ligand.