Nitrile-functionalized ruthenium nanoparticles: charge delocalization through Ru − N ≡ C interface

Research Paper
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Abstract

Ruthenium nanoparticles (2.06 ± 0.46 nm in diameter) were stabilized by the self-assembly of nitrile molecules onto the ruthenium colloid surface by virtue of the formation of Ru−N≡C interfacial bonding linkages. Thermogravimetric analysis showed that there were about 63 nitrile ligands per nanoparticle, corresponding to an average molecular footprint of 22.4 Å2. Proton nuclear magnetic resonance (NMR) studies suggested an end-on configuration of the nitrile moiety on the metal core surface. Meanwhile, infrared measurements showed that the C≡N stretch red-shifted from 2246 to 1944 cm−1 upon adsorption on the nanoparticle surfaces, as confirmed by 15N isotopic labeling. This apparent red-shift suggests extensive intraparticle charge delocalization, which was further manifested by photoluminescence measurements of 1-cyanopyrene-functionalized ruthenium nanoparticles that exhibited a red shift of 40 nm of the emission maximum, in comparison to that of free monomers. The results further highlight the significance of metal−organic contacts in the manipulation of the dynamics of intraparticle charge transfer and the nanoparticle optical and electronic properties.

Graphical abstract

Keywords

Ruthenium nanoparticles Nitrile Metal-organic interfacial bond Intraparticle charge delocalization 
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Notes

Acknowledgments

This work was supported by the National Recruitment Program of Global Experts. X. W. K. acknowledges the financial support from South China University of Technology. S. W. C. also thank the National Science Foundation for the partial support of the work (CHE-1265635 and DMR-1409396).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

11051_2017_3801_MOESM1_ESM.docx (1.5 mb)
ESM 1 FTIR, 1H NMR and MS spectra of di-EPy, representative TEM micrograph and core size histogram of RuNC12 nanoparticles, XPS full survey of NC12 and RuNC12 nanoparticles and excitation and emission spectra of EPy, di-EPy and RuEPy. (DOCX 50 kb)

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Copyright information

© Springer Science+Business Media Dordrecht 2017

Authors and Affiliations

  1. 1.New Energy Research Institute, School of Environment and Energy, Guangzhou Higher Education Mega CentreSouth China University of TechnologyGuangzhouChina
  2. 2.School of Bioscience and Bioengineering, Guangzhou Higher Education Mega CentreSouth China University of TechnologyGuangzhouChina
  3. 3.Department of Chemistry and BiochemistryUniversity of CaliforniaSanta CruzUSA

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