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Award Detail

Awardee:CORNELL UNIVERSITY
Doing Business As Name:Cornell University
PD/PI:
  • Hector D Abruna
  • (607) 255-4720
  • hda1@cornell.edu
Award Date:09/22/2008
Estimated Total Award Amount: $ 1,500,000
Funds Obligated to Date: $ 1,519,821
  • FY 2009=$19,821
  • FY 2010=$350,000
  • FY 2008=$1,150,000
Start Date:10/01/2008
End Date:09/30/2012
Transaction Type:Grant
Agency:NSF
Awarding Agency Code:4900
Funding Agency Code:4900
CFDA Number:47.049
Primary Program Source:040100 NSF RESEARCH & RELATED ACTIVIT
Award Title or Description:CCI Phase I: Center for Molecular Interfacing
Federal Award ID Number:0847926
DUNS ID:872612445
Parent DUNS ID:002254837
Program:CHE CENTERS
Program Officer:
  • Katharine Covert
  • (703) 292-4950
  • kcovert@nsf.gov

Awardee Location

Street:373 Pine Tree Road
City:Ithaca
State:NY
ZIP:14850-2820
County:Ithaca
Country:US
Awardee Cong. District:23

Primary Place of Performance

Organization Name:Cornell University
Street:373 Pine Tree Road
City:Ithaca
State:NY
ZIP:14850-2820
County:Ithaca
Country:US
Cong. District:23

Abstract at Time of Award

The Center for Molecular Interfacing (CMI) will enable the integration of well-controlled molecular constituents within macroscopic systems by using graphene sheets and carbon nanotubes (CNTs) to achieve molecularly well-defined, reproducible and robust connections. This interdisciplinary and inter-institutional team of researchers will (1) study electrical and opto-electronic properties of graphene-molecule-graphene and CNT-molecule-CNT devices with mechanical adjustability, electrolytic gating, and optical access; (2) use AFM and STM to characterize the molecule-graphene interface; and (3) use advanced laser microscopy to identify and excite individual electrically-contacted molecules. This work will be enabled by the development of novel experimental platforms and techniques, synthesis of molecular architectures of deliberate design and function, and the development of a theoretical framework. Fundamental chemical processes such as self-exchange rates in redox reactions, the distance dependence of electron transfer, and photoinduced electron transfer can all be studied by precisely modulating the spacing in graphene-molecule-graphene structures. These studies will provide the knowledge base to enable revolutionary advances in technologies such as energy conversion and storage, sensing, information technologies, and catalysis. The proposed work combines chemistry and physics at the cutting edge of science and technology and provides students with collaborative interdisciplinary research training. Particular emphasis will be placed in the recruitment and retention of women and underrepresented minorities at all educational levels. Young children in Puerto Rico will participate in a novel bilingual outreach program "Molecules meet Macro" in partnership with the Casa Pueblo Cooperative in Adjuntas, Puerto Rico. Center researchers will also participate in local news features, demonstrations and exhibits at a local science museum, and other public outreach projects. The Centers for Chemical Innovation (CCI) Program supports research centers that can address major, long-term fundamental chemical research challenges that have a high probability of both producing transformative research and leading to innovation. These Centers will attract broad scientific and public interest.

Publications Produced as a Result of this Research

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Neus Vila, Yu-Wu Zhong, Jay C. Henderson and Hector D. Abruna "Binuclear Ruthenium Complexes Based on Anthracene Derivatives as Bridging Ligands: Electrochemical and Spectroscopic Evidences of an Electronic Communication through the Pi-System" Inorganic Chemistry, v.49(3), 2010, p.796.

Rodriguez-Lopez, Joaquin; Ritzert, Nicole L.; Mann, Jason A.; Tan, Cen; Dichtel, William R.; Abruna, Hector D. "Quantification of the Surface Diffusion of Tripodal Binding Motifs on Graphene Using Scanning Electrochemical Microscopy" JACS, v.134, 2012, p.6224.

Neus Vila, Yu-Wu Zhong, Jay C. Henderson, and Hector D. Abruna "Anthracene-Bridged Binuclear Ruthenium Complexes: Electrochemical and Spectroscopic Evidence of Electronic Communication Through the Pi-System" Inorganic Chemistry, v.49, 2009, p.796-804. doi:10.1021/ic900100w 

Arend M. van der Zande, Robert A. Barton, Jonathan S. Alden, Carlos S. Ruiz-Vargas, William S. Whitney, Phi H.Q. Pham, Jiwoong Park, Jeevak M. Parpia, Harold G. Craighead, and Paul L. McEuen "Large-scale arrays of single-layer graphene resonators" Nanoletters, v.10, 2010, p.4869.

Daniel Y. Joh, Jesse Kinder, Lihong H. Herman, Sang-Yong Ju, Michael A. Segal, Jeffreys N. Johnson, Garnet K.-L. Chan & Jiwoong Park "Single-walled carbon nanotubes as excitonic optical wires" Nature Nanotechnology, v.6, 2011, p.51-56. doi:10.1038/nnano.2010.248 

Cen Tan, Joaquin Rodriguez-Lopez, Joshua J. Parks, Nicole L. Ritzert, Daniel C. Ralph, and Hector D. Abruna "Reactivity of Monolayer Chemical Vapor Deposited Graphene Imperfections Studied Using Scanning Electrochemical Microscopy" ACS Nano, v.6, 2012, p.3070-3079. doi:10.1021/nn204746n 

Eric L. Spitler and William R. Dichtel "Lewis acid-catalysed formation of two-dimensional phthalocyanine covalent organic frameworks" Nature Chemistry, v.2, 2010, p.672-677. doi:10.1038/nchem.695 

Nicole L. Ritzert, Joaquin Rodriguez-Lopez, Cen Tan, and Hector D. Abruna "Kinetics of Interfacial Electron Transfer at Single Layer Graphene Electrodes in Aqueous and Non-Aqueous Solutions" Langmuir, v.29, 2013, p.1683-1694. doi:10.1021/la3042549 

Mann, J. A.; Rodriguez-Lopez, J. Abruna, H. D.; Dichtel, W. R. "Multivalent Binding Motifs for the Noncovalent Functionalization of Graphene" JACS, v.133, 2011, p.17614.

Jason A. Mann, Joaquin Rodriguez-Lopez, Hector D. Abruna, and William R. Dichtel "Multivalent Binding Motifs for the Noncovalent Functionalization of Graphene" Journal of the American Chemical Society, v.133, 2011, p.17614-176. doi:10.1021/ja208239v 

San-Huang Ke, Rui Lui, Weitao Yang, and Harold U. Baranger "Time-dependent transport through molecular junctions" Journal of Chemical Physics, v.132, 2010, p.234105. doi:10.1063/1.3435351 

Xiao Zheng, San-Huang Ke and Weitao Yang "Conductive Graphene-Molecule-Graphene Junctions" Journal of Chemical Physics, v.132(11), 2010, p..

Ke SH, Liu R, Yang W, Baranger H. U. "Time-dependent transport through molecular junctions" Journal of Chemical Physics, v.132, 2010, p.234105.

Eugenia S. Tam, Joshua J. Parks, William W. Shum, Yu-Wu Zhong, Mitk'El Santiago-Berrios, Xiao Zheng, Weitao Yang, Garnet K.-L. Chan, Hector D. Abruna, and Daniel C. Ralph "Single-Molecule Conductance of Pyridine-Terminated Dithienylethene Switch Molecules" ACS Nano, v.5, 2011, p.5115-5123. doi:10.1021/nn201199b 

Si-Hai Wu, Stephen E. Burkhardt, Jiannian Yao, Yu-Wu Zhong, Hector D. Abruna "Near-Infrared Absorbing and Emitting Ru(II)-Pt(II) Heterodimetallic Complexes of Dpdpz (Dpdpz = 2,3-Di(2-pyridyl)-5,6-diphenylpyrazine)" Inorganic Chemistry, v.50, 2011, p.3959-3969. doi:10.1021/ic1023696 

Zheng, X; Ke, SH; Yang, WT "Conductive junctions with parallel graphene sheets" JOURNAL OF CHEMICAL PHYSICS, v.132, 2010, p.. doi:10.1063/1.335741  View record at Web of Science

Xiao Zheng, San-Huang Ke, and Weitao Yang "Conductive junctions with parallel graphene sheets" Journal of Chemical Physics, v.132, 2010, p.114703/1. doi:10.1063/1.3357416 

Joaquin Rodriguez-Lopez, Nicole L. Ritzert, Jason A. Mann, Cen Tan, William R. Dichtel and Hector D. Abruna "Quantification of the Surface Diffusion of Tripodal Binding Motifs on Graphene Using Scanning Electrochemical Microscopy" Journal of the American Chemical Society, v.134, 2012, p.6224-6236. doi:10.1021/ja2106724 

Si-Hai Wu, Stephen E. Burkhardt, Yu-Wu Zhong, Hector D. Abruna "Cyclometalated Ruthenium Oligomers with 2,3-Di(2-pyridyl)-5,6-diphenylpyrazine: A Combined Experimental, Computational, and Comparison Study with Noncyclometalated Analogous" Inorganic Chemistry, v.51, 2012, p.13312-133. doi:10.1021/ic3019666 

Joh, DY; Herman, LH; Ju, SY; Kinder, J; Segal, MA; Johnson, JN; Chan, GKL; Park, J "On-Chip Rayleigh Imaging and Spectroscopy of Carbon Nanotubes" NANO LETTERS, v.11, 2011, p.1. doi:10.1021/nl101256  View record at Web of Science

Arend M. van der Zande, Robert A. Barton, Jonathan S. Alden, Carlos S. Ruiz-Vargas, William S. Whitney, Phi H. Q. Pham, Jiwoong Park, Jeevak M. Parpia, Harold G. Craighead, and Paul L. McEuen "Large-scale arrays of single-layer graphene resonators" Nano Letters, v.10, 2010, p.4869-4873. doi:10.1021/nL102713c 

Daniel Y. Joh, Lihong H. Herman, Sang-Yong Ju, Jesse Kinder, Michael A. Segal, Jeffreys N. Johnson, Garnet K. L. Chan, and Jiwoong Park "On-Chip Rayleigh Imaging and Spectroscopy of Carbon Nanotubes" Nano Letters, v.11, 2010, p.1-7. doi:10.1021/nl1012568 

Tan, Cen; Rodriguez-Lopez, Joaquin; Parks, Joshua J.; Ritzert, Nicole L.; Ralph, Daniel C.; Abruna, Hector D. "Reactivity of Monolayer Chemical Vapor Deposited Graphene Imperfections Studied Using Scanning Electrochemical Microscopy" ACS Nano, v.6, 2012, p.3070.

Tam, Eugenia S.; Parks, Joshua J.; Shum, William W.; Zhong, Yu-Wu; Santiago-Berrios, Mitk'El B.; Zheng, Xiao; Yang, Weitao; Chan, Garnet K.-L.; Abruna, Hector D.; Ralph, Daniel C. "Single-Molecule Conductance of Pyridine-Terminated Dithienylethene Switch Molecules" ACS Nano, v.5, 2011, p.5115.

Yu-Wu Zhong, Si-Hai Wu, Stephen E. Burkhardt, Chang-Jiang Yao, Hector D. Abruna "Mononuclear and Dinuclear Ruthenium Complexes of 2,3-Di-2-pyridyl-5,6-diphenylpyrazine: Synthesis and Spectroscopic and Electrochemical Studies" Inorganic Chemistry, v.50, 2011, p.517-524. doi:10.1021/ic101629w 

Joh, DY; Kinder, J; Herman, LH; Ju, SY; Segal, MA; Johnson, JN; Chan, GKL; Park, J "Single-walled carbon nanotubes as excitonic optical wires" NATURE NANOTECHNOLOGY, v.6, 2011, p.51. doi:10.1038/NNANO.2010.24  View record at Web of Science


Project Outcomes Report

Disclaimer

This Project Outcomes Report for the General Public is displayed verbatim as submitted by the Principal Investigator (PI) for this award. Any opinions, findings, and conclusions or recommendations expressed in this Report are those of the PI and do not necessarily reflect the views of the National Science Foundation; NSF has not approved or endorsed its content.

The main objective of our Phase-I Center for Chemical Innovation, the Center for Molecular Interfacing (CMI) was to enable the integration of well-controlled molecular constituents within macroscopic systems by using graphene sheets and CNTs to achieve molecularly well-defined, reproducible and robust connections. Our work involved a combination of synthesis of molecular architectures of deliberate design and function, the development of novel experimental platforms and techniques, and the development of theory and simulation to provide a theoretical framework. While we were not successful in advancing to a Phase II Center, we nonetheless feel that we made very significant advances.

Below we present a summary of the most salient findings of our last year of
support. The report presents findings in the areas of synthesis and characterization of graphene layers, carbon nanotubes and assemblies followed by computational studies.
1. Carbon Nanotubes and Graphene:

A. On-chip Rayleigh imaging of carbon nanotubes Carbon nanotubes are a heterogeneous group of materials. As-grown carbon nanotubes can comprise single-walled carbon nanotubes (SWNTs) with a wide range of structural (n, m) indices, multi-walled carbon nanotubes (MWNTs), nanotube bundles, and SWNTs that change chirality due to structural defects. Furthermore, their interactions with the environment and other neighbouring nanotubes directly affect their electronic and optical properties. Previously demonstrated characterization methods, including transmission electron microscopy, scanning tunnelling microscopy and various optical spectroscopic techniques, usually require long data acquisition times and/or complicated sample preparation, which limits their use as a general characterization method for SWNTs.

Optical imaging of carbon nanotubes placed directly on a solid substrate allows rapid visualization and spectral resolution of individual nanotubes with relative ease. We reported a novel on-chip Rayleigh imaging technique using wide-field laser illumination to measure optical scattering of an array of individual SWNTs on a solid substrate with high spatial and spectral resolution.  This method, in conjunction with calibrated AFM measurements, accurately measures the resonance energies and  diameters for a large number of SWNTs in parallel. We applied this technique for fast mapping of key SWNT parameters, including the electronic-types and chiral indices for individual SWNTs, position and frequency of chirality-changing events, and intertube interactions in both bundled and distant SWNTs. This work was published in Nano Letters as a cover article in Jan 2011. [1]

B. SWNTs as Excitonic Optical Wires
Although metallic nanostructures are useful for nanoscale optics, all of their key optical properties are determined by their geometry. This makes it difficult to adjust these properties independently, and can restrict applications. Recently, we used absolute intensity of Rayleigh scattering to show that SWNTs can form ideal optical wires. [2]  The spatial distribution of the radiation scattered by the nanotubes is determined by their shape, but the intensity and spectrum of the scattered radiation are determined by exciton dynamics, quantum-dot-like optical resonances and other intrinsic properties.  Moreover, the nanotubes display a uniform peak optical conductivity ~ 8 e2/h, which we derived using an exciton model, suggesting universal behaviour similar to that observed in nanotube conductance. Combined, these properties make single-walled carbon nanotubes prototypical one-dimensional optical nanostructures, or excitonic optical wires, whose spectral response is mainly controlled by the intrinsic quantum-mechanical properties of the material, while the scattered field can be independently determined by their shape. We further demonstrated a radiative ...

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