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Assembly, characterization, and electrochemical properties of immobilized metal bipyridyl complexes on silicon(111) surface

Lattimer, Judith R. C. and Blakemore, James D. and Sattler, Wesley and Gul, Sheraz and Chatterjee, Ruchira and Yachandra, Vittal K. and Yano, Junko and Brunschwig, Bruce S. and Lewis, Nathan S. and Gray, Harry B. (2014) Assembly, characterization, and electrochemical properties of immobilized metal bipyridyl complexes on silicon(111) surface. Dalton Transactions, 43 (40). pp. 15004-15012. ISSN 1477-9226.

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Silicon(111) surfaces have been functionalized with mixed monolayers consisting of submonolayer coverages of immobilized 4-vinyl-2,2′-bipyridyl (1, vbpy) moieties, with the remaining atop sites of the silicon surface passivated by methyl groups. As the immobilized bipyridyl ligands bind transition metal ions, metal complexes can be assembled on the silicon surface. X-ray photoelectron spectroscopy (XPS) demonstrates that bipyridyl complexes of [Cp*Rh], [Cp*Ir], and [Ru(acac)2] were formed on the surface (Cp* is pentamethylcyclopentadienyl, acac is acetylacetonate). For the surface prepared with Ir, X-ray absorption spectroscopy at the Ir LIII edge showed an edge energy as well as post-edge features that were essentially identical with those observed on a powder sample of [Cp*Ir(bpy)Cl]Cl (bpy is 2,2′-bipyridyl). Charge-carrier lifetime measurements confirmed that the silicon surfaces retain their highly favorable photoelectronic properties upon assembly of the metal complexes. Electrochemical data for surfaces prepared on highly doped, n-type Si(111) electrodes showed that the assembled molecular complexes were redox active. However the stability of the molecular complexes on the surfaces was limited to several cycles of voltammetry.

Item Type:Article
Related URLs:
URLURL TypeDescription
Blakemore, James D.0000-0003-4172-7460
Sattler, Wesley0000-0001-5316-260X
Gul, Sheraz0000-0001-8920-8737
Chatterjee, Ruchira0000-0002-0865-061X
Yano, Junko0000-0001-6308-9071
Brunschwig, Bruce S.0000-0002-6135-6727
Lewis, Nathan S.0000-0001-5245-0538
Gray, Harry B.0000-0002-7937-7876
Additional Information:© 2014 Royal Society of Chemistry. Advance Article. Received 18th April 2014; Accepted 9th July 2014. First published online 17 Jul 2014. The authors thank Aaron Sattler for helpful discussions. Research was carried out in part at the Molecular Materials Research Center of the Beckman Institute at the California Institute of Technology. This work was supported by the NSF CCI Solar Fuels Program (CHE-1305124) and CCI Postdoctoral Fellowships to JDB and WS. The synchrotron facility was provided by the Stanford Synchrotron Radiation Laboratory (SSRL) at beam line 7-3. The SSRL Biomedical Technology program is supported by the National Institute of Health (NIH), the National Center for Research Resources, and the DOE Office of Biological and Environmental Research. XAS work was funded by the Director, Office of Science, Office of Basic Energy Sciences (OBES), Division of Chemical Sciences, Geosciences, and Biosciences of the Department of Energy (DOE) under Contract DE-AC02-05CH11231.
Group:CCI Solar Fuels
Funding AgencyGrant Number
NSF Postdoctoral FellowshipUNSPECIFIED
Department of Energy (DOE)DE-AC02-05CH11231
Issue or Number:40
Record Number:CaltechAUTHORS:20140721-090909176
Persistent URL:
Official Citation:Lattimer, J. R. C., Blakemore, J. D., Sattler, W., Gul, S., Chatterjee, R., Yachandra, V. K., . . . Gray, H. B. (2014). Assembly, characterization, and electrochemical properties of immobilized metal bipyridyl complexes on silicon(111) surfaces. [10.1039/C4DT01149J]. Dalton Transactions. doi: 10.1039/c4dt01149j
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:47359
Deposited By: Jason Perez
Deposited On:21 Jul 2014 19:02
Last Modified:02 Mar 2020 23:32

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