Rooney, P.; Rezaee, A.;Xu, S.; Manifar, T.; and Rangan, Chitra. (2008 We present experimental and theoretical results for the changes in the optical-plasmon resonance of goldnanoparticle dimers immobilized on a surface when coated with an organic dielectric material. The plasmon band of a nanoparticle dimer shifts to a higher wavelength when the distance between neighboring particles is decreased, and a well-separated second peak appears. This phenomenon is called cross-talk. We find that an organic coating lets cross-talk start at larger separation distances than for uncoated dimers by bridging the gap between immobilized nanoparticles ͑creating optical clusters͒. We study this optical clustering effect as a function of the polarization of the applied light, of the inter-particle distance, of the surrounding environment, and of the optical properties of the coating layer. Theoretical discrete-dipole approximation calculations support the experimental absorption spectroscopy results of gold nanoparticles on glass substrates and on optical waveguides.
Various calix[4]arene derivatives, fixed in the cone conformation by decylether groups and functionalized at their wide rim by urea residues, were synthesized. In two compounds (,) sulfur functions were attached to the urea groups via different spacers in order to allow binding to metal surfaces. While they exist as single molecules in polar solvents, tetraurea calix[4]arenes of this type () combine to form dimeric capsules in aprotic, apolar solvents. A solvent molecule is usually included in such a capsule, if no guest with a higher affinity is present. In the presence of an equimolar amount of the tetratosylurea, the exclusive formation of heterodimers, consisting of one molecule of and, is observed. The homo- and heterodimerization of the newly prepared derivatives, were studied by 1H NMR to establish the conditions under which they exhibit the desired dimerization behaviour. Self-assembled monolayers (SAMs) were formed using the single calix[4]arenes, and the heterodimeric capsules. Chloroform, dichloromethane and ferrocenium cations were used as guests in these immobilized heterodimeric capsules. The particular supramolecular architecture of the heterodimers should ensure that, after the immobilization on the metal surface, decomposition of the capsules and release or exchange of the guest is impossible or at least hindered. The self-assembly process and the stability of SAMs formed by capsules filled with ferrocenium cations in electrolyte solutions were tested with surface plasmon spectroscopy. The inclusion of guests, such as dichloromethane or ferrocenium, in the immobilized capsules were confirmed by classical surface plasmon spectroscopy, by gold nanoparticle absorption spectroscopy and by time-of flight secondary ion mass spectrometry (ToF-SIMS). The film stability and quality was tested by cyclic voltammetry.
Octamethoxy calix[8]arenes substituted in the para position by amide, urea, and imide functions were synthesized from the octamethyl ether of tert-butylcalix[8]arene by ipso nitration, reduction, and acylation. Scanning force microscopy of spin coated samples on graphite suggests that these derivatives self-organize into tubular nanorods via hydrogen bonds between p-amide functions. A single-crystal X-ray structure reveals a centrosymmetric conformation for the octanitro derivative. [structure: see text]
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