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Multi-photon patterning of photoactive o-nitrobenzyl ligands bound to gold surfaces

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dc.contributor.authorMagill, Brenden A.en
dc.contributor.authorGuo, Xien
dc.contributor.authorPeck, Cheryl L.en
dc.contributor.authorReyes, Roberto L.en
dc.contributor.authorSee, Erich M.en
dc.contributor.authorSantos, Webster L.en
dc.contributor.authorRobinson, Hans D.en
dc.contributor.departmentChemistryen
dc.contributor.departmentPhysicsen
dc.date.accessioned2019-06-06T14:24:39Zen
dc.date.available2019-06-06T14:24:39Zen
dc.date.issued2019-01-01en
dc.date.updated2019-06-06T14:10:41Zen
dc.description.abstractWe quantitatively investigate lithographic patterning of a thiol-anchored self-assembled monolayer (SAM) of photocleavable o-nitrobenzyl ligands on gold through a multi-photon absorption process at 1.7 eV (730 nm wavelength). The photocleaving rate increases faster than the square of the incident light intensity, indicating a process more complex than simple two-photon absorption. We tentatively ascribe this observation to two-photon absorption that triggers the formation of a long-lived intermediate aci-nitro species whose decomposition yield is partially determined either by absorption of additional photons or by a local temperature that is elevated by the incident light. At the highest light intensities, thermal processes compete with photoactivation and lead to damage of the SAM. The threshold is high enough that this destructive process can largely be avoided, even while power densities are kept sufficiently large that complete photoactivation takes place on time scales of tens of seconds to a few minutes. This means that this type of ligand can be activated at visible and near infrared wavelengths where plasmonic resonances can easily be engineered in metal nanostructures, even though their single-photon reactivity at these wavelengths is negligible. This will allow selective functionalization of plasmon hotspots, which in addition to high resolution lithographic applications would be of benefit to applications such as Surface Enhanced Raman Spectroscopy and plasmonic photocatalysis as well as directed bottom-up nanoassembly.en
dc.description.versionPublished versionen
dc.format.extentPages 30-44en
dc.format.extent15 page(s)en
dc.format.mediumPrint-Electronicen
dc.format.mimetypeapplication/pdfen
dc.identifier.doihttps://doi.org/10.1039/c8pp00346gen
dc.identifier.eissn1474-9092en
dc.identifier.issn1474-905Xen
dc.identifier.issue1en
dc.identifier.orcidSantos, Webster [0000-0002-4731-8548]en
dc.identifier.orcidRobinson, Hans [0000-0003-3928-105X]en
dc.identifier.pmid30346005en
dc.identifier.urihttp://hdl.handle.net/10919/89890en
dc.identifier.volume18en
dc.language.isoenen
dc.publisherRoyal Society of Chemistryen
dc.relation.urihttp://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000457260400027&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=930d57c9ac61a043676db62af60056c1en
dc.rightsIn Copyrighten
dc.rights.urihttp://rightsstatements.org/vocab/InC/1.0/en
dc.subjectScience & Technologyen
dc.subjectLife Sciences & Biomedicineen
dc.subjectPhysical Sciencesen
dc.subjectBiochemistry & Molecular Biologyen
dc.subjectBiophysicsen
dc.subjectChemistry, Physicalen
dc.subjectChemistryen
dc.subjectSELF-ASSEMBLED MONOLAYERSen
dc.subjectPHOTOCHEMICAL-REACTION MECHANISMSen
dc.subjectPHOTOREMOVABLE PROTECTING GROUPSen
dc.subject2-NITROBENZYL COMPOUNDSen
dc.subject2-PHOTON POLYMERIZATIONen
dc.subjectCROSS-SECTIONSen
dc.subjectIMMOBILIZATIONen
dc.subjectRESOLUTIONen
dc.subjectPHOTOLITHOGRAPHYen
dc.subject2-NITROTOLUENEen
dc.subject0306 Physical Chemistry (Incl. Structural)en
dc.subject0601 Biochemistry And Cell Biologyen
dc.subject0299 Other Physical Sciencesen
dc.subjectOrganic Chemistryen
dc.titleMulti-photon patterning of photoactive o-nitrobenzyl ligands bound to gold surfacesen
dc.title.serialPhotochemical & Photobiological Sciencesen
dc.typeArticle - Refereeden
dc.type.dcmitypeTexten
dc.type.otherArticleen
dc.type.otherJournalen
pubs.organisational-group/Virginia Tech/Scienceen
pubs.organisational-group/Virginia Techen
pubs.organisational-group/Virginia Tech/All T&R Facultyen
pubs.organisational-group/Virginia Tech/Science/Physicsen
pubs.organisational-group/Virginia Tech/Science/COS T&R Facultyen
pubs.organisational-group/Virginia Tech/Faculty of Health Sciencesen
pubs.organisational-group/Virginia Tech/Science/Chemistryen
pubs.organisational-group/Virginia Tech/University Research Institutes/Fralin Life Sciences/Chloe Lahondereen
pubs.organisational-group/Virginia Tech/University Research Institutes/Fralin Life Sciencesen
pubs.organisational-group/Virginia Tech/University Research Institutesen

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