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

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.

doi:10.1039/C5SC01474C

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

Journal Article · Tue Jul 28 00:00:00 EDT 2015 · Chemical Science

DOI:https://doi.org/10.1039/C5SC01474C· OSTI ID:1214424

Rosen, Evelyn L. ^[1]; Gilmore, Keith ^[1]; Sawvel, April M. ^[1]; Hammack, Aaron T. ^[1]; Doris, Sean E. ^[2]; Aloni, Shaul ^[1]; Altoe, Virginia ^[1]; Nordlund, Dennis ^[3]; Weng, Tsu -Chien ^[3]; Sokaras, Dimosthenis ^[3]; Cohen, Bruce E. ^[1]; Urban, Jeffrey J. ^[1]; Ogletree, D. Frank ^[1]; Milliron, Delia J. ^[4]; Prendergast, David ^[1]; Helms, Brett A. ^[1]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); The Univ. of Texas at Austin, Austin, TX (United States)

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.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Workforce Development for Teachers and Scientists (WDTS)

Grant/Contract Number:: AC02-05CH11231; AC02-76SF00515

OSTI ID:: 1214424

Alternate ID(s):: OSTI ID: 1215393

Journal Information:: Chemical Science, Vol. 6, Issue 11; ISSN 2041-6520

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 1 work

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