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Title: Chemically directing d-block heterometallics to nanocrystal surfaces as molecular beacons of surface structure

Abstract

Our understanding of structure and bonding in nanoscale materials is incomplete without knowledge of their surface structure. Needed are better surveying capabilities responsive not only to different atoms at the surface, but also their respective coordination environments. We report here that d-block organometallics, when placed at nanocrystal surfaces through heterometallic bonds, serve as molecular beacons broadcasting local surface structure in atomic detail. This unique ability stems from their elemental specificity and the sensitivity of their d-orbital level alignment to local coordination environment, which can be assessed spectroscopically. Re-surfacing cadmium and lead chalcogenide nanocrystals with iron- or ruthenium-based molecular beacons is readily accomplished with trimethylsilylated cyclopentadienyl metal carbonyls. For PbSe nanocrystals with iron-based beacons, we show how core-level X-ray spectroscopies and DFT calculations enrich our understanding of both charge and atomic reorganization at the surface when beacons are bound.

Authors:
 [1];  [1];  [1];  [1];  [2];  [1];  [1];  [3];  [3];  [3];  [1];  [1];  [1];  [4];  [1];  [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); The Univ. of Texas at Austin, Austin, TX (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Science (SC), Workforce Development for Teachers and Scientists (WDTS) (SC-27)
OSTI Identifier:
1214424
Alternate Identifier(s):
OSTI ID: 1215393
Grant/Contract Number:  
AC02-05CH11231; AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 6; Journal Issue: 11; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 77 NANOSCIENCE AND NANOTECHNOLOGY; 36 MATERIALS SCIENCE

Citation Formats

Rosen, Evelyn L., Gilmore, Keith, Sawvel, April M., Hammack, Aaron T., Doris, Sean E., Aloni, Shaul, Altoe, Virginia, Nordlund, Dennis, Weng, Tsu -Chien, Sokaras, Dimosthenis, Cohen, Bruce E., Urban, Jeffrey J., Ogletree, D. Frank, Milliron, Delia J., Prendergast, David, and Helms, Brett A. Chemically directing d-block heterometallics to nanocrystal surfaces as molecular beacons of surface structure. United States: N. p., 2015. Web. doi:10.1039/C5SC01474C.
Rosen, Evelyn L., Gilmore, Keith, Sawvel, April M., Hammack, Aaron T., Doris, Sean E., Aloni, Shaul, Altoe, Virginia, Nordlund, Dennis, Weng, Tsu -Chien, Sokaras, Dimosthenis, Cohen, Bruce E., Urban, Jeffrey J., Ogletree, D. Frank, Milliron, Delia J., Prendergast, David, & Helms, Brett A. Chemically directing d-block heterometallics to nanocrystal surfaces as molecular beacons of surface structure. United States. doi:10.1039/C5SC01474C.
Rosen, Evelyn L., Gilmore, Keith, Sawvel, April M., Hammack, Aaron T., Doris, Sean E., Aloni, Shaul, Altoe, Virginia, Nordlund, Dennis, Weng, Tsu -Chien, Sokaras, Dimosthenis, Cohen, Bruce E., Urban, Jeffrey J., Ogletree, D. Frank, Milliron, Delia J., Prendergast, David, and Helms, Brett A. Tue . "Chemically directing d-block heterometallics to nanocrystal surfaces as molecular beacons of surface structure". United States. doi:10.1039/C5SC01474C. https://www.osti.gov/servlets/purl/1214424.
@article{osti_1214424,
title = {Chemically directing d-block heterometallics to nanocrystal surfaces as molecular beacons of surface structure},
author = {Rosen, Evelyn L. and Gilmore, Keith and Sawvel, April M. and Hammack, Aaron T. and Doris, Sean E. and Aloni, Shaul and Altoe, Virginia and Nordlund, Dennis and Weng, Tsu -Chien and Sokaras, Dimosthenis and Cohen, Bruce E. and Urban, Jeffrey J. and Ogletree, D. Frank and Milliron, Delia J. and Prendergast, David and Helms, Brett A.},
abstractNote = {Our understanding of structure and bonding in nanoscale materials is incomplete without knowledge of their surface structure. Needed are better surveying capabilities responsive not only to different atoms at the surface, but also their respective coordination environments. We report here that d-block organometallics, when placed at nanocrystal surfaces through heterometallic bonds, serve as molecular beacons broadcasting local surface structure in atomic detail. This unique ability stems from their elemental specificity and the sensitivity of their d-orbital level alignment to local coordination environment, which can be assessed spectroscopically. Re-surfacing cadmium and lead chalcogenide nanocrystals with iron- or ruthenium-based molecular beacons is readily accomplished with trimethylsilylated cyclopentadienyl metal carbonyls. For PbSe nanocrystals with iron-based beacons, we show how core-level X-ray spectroscopies and DFT calculations enrich our understanding of both charge and atomic reorganization at the surface when beacons are bound.},
doi = {10.1039/C5SC01474C},
journal = {Chemical Science},
number = 11,
volume = 6,
place = {United States},
year = {2015},
month = {7}
}

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