Multifunctional and Stable Monolayers on Carbon: A Simple and Reliable Method for Backfilling Sparse Layers Grafted from Protected Aryldiazonium Ions

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dc.contributor.authorLee L
dc.contributor.authorGunby NR
dc.contributor.authorDownard AJ
dc.contributor.authorCrittenden, Deborah
dc.contributor.authorDownard, Alison
dc.date.accessioned2023-03-22T23:42:22Z
dc.date.available2023-03-22T23:42:22Z
dc.date.issued2016en
dc.date.updated2023-02-13T02:39:52Z
dc.description.abstractA new strategy for preparation of robust multifunctional low nanometer thickness monolayers on carbon substrates is presented. Beginning with protected aryldiazonium salts, sparse monolayers of ethynyl-, amino-, and carboxy-terminated tethers are covalently anchored to the surface. The layers are then backfilled with a second modifier via the nucleophilic addition of an amine derivative to the surface. Through use of electroactive moieties coupled to the tethers, and an electroactive amine for backfilling, electrochemical measurements reveal that backfilling approximately doubles the surface concentration of the monolayer. Cyclic voltammetry of solution-based redox probes at the modified surfaces is consistent with the expected blocking properties at various stages of surface preparation. Fractional surface coverages of the layers are estimated using electrochemically determined surface concentrations of modifiers and computationally derived modifier footprints. Assuming free rotation of the coupled ferrocenyl or nitrophenyl groups leads to physically unreasonable fractional surface coverages, indicating that these larger modifiers must be rotationally restricted. Using a conformationally constrained model produces lower bound estimates of the total fractional surface coverage close to 0.4, with tether-only coverages close to 0.2. The backfilled tether layers constitute practical platforms for controlled construction of complex interfaces with many potential applications including sensing, molecular electronics, and catalysis.en
dc.identifier.citationLee L, Gunby NR, Crittenden DL, Downard AJ (2016). Multifunctional and Stable Monolayers on Carbon: A Simple and Reliable Method for Backfilling Sparse Layers Grafted from Protected Aryldiazonium Ions. Langmuir. 32(11). 2626-2637.en
dc.identifier.doihttp://doi.org/10.1021/acs.langmuir.5b04546
dc.identifier.issn0743-7463
dc.identifier.issn1520-5827
dc.identifier.urihttps://hdl.handle.net/10092/105280
dc.languageEnglish
dc.language.isoenen
dc.publisherAMER CHEMICAL SOCen
dc.rightsAll rights reserved unless otherwise stateden
dc.rights.urihttp://hdl.handle.net/10092/17651en
dc.subjectScience & Technologyen
dc.subjectPhysical Sciencesen
dc.subjectTechnologyen
dc.subjectChemistry, Multidisciplinaryen
dc.subjectChemistry, Physicalen
dc.subjectMaterials Science, Multidisciplinaryen
dc.subjectChemistryen
dc.subjectMaterials Scienceen
dc.subjectELECTRON-TRANSFER KINETICSen
dc.subjectATOMIC-FORCE MICROSCOPYen
dc.subjectGLASSY-CARBONen
dc.subjectDIAZONIUM SALTSen
dc.subjectCOVALENT MODIFICATIONen
dc.subjectARYL RADICALSen
dc.subjectELECTROCHEMICAL BIOSENSORSen
dc.subjectSURFACE MODIFICATIONen
dc.subjectTERMINAL ALKYNESen
dc.subjectREDUCTIONen
dc.subjectnucleophilic additionen
dc.subjectamineen
dc.subjectclick reactionen
dc.subjectamide couplingen
dc.subjectDFTen
dc.subjectfractional coverageen
dc.subject.anzsrcFields of Research::34 - Chemical sciences::3403 - Macromolecular and materials chemistry::340303 - Nanochemistryen
dc.subject.anzsrcFields of Research::34 - Chemical sciences::3403 - Macromolecular and materials chemistry::340309 - Theory and design of materialsen
dc.subject.anzsrcFields of Research::34 - Chemical sciences::3406 - Physical chemistry::340603 - Colloid and surface chemistryen
dc.subject.anzsrcFields of Research::40 - Engineering::4016 - Materials engineering::401699 - Materials engineering not elsewhere classifieden
dc.titleMultifunctional and Stable Monolayers on Carbon: A Simple and Reliable Method for Backfilling Sparse Layers Grafted from Protected Aryldiazonium Ionsen
dc.typeJournal Articleen
uc.collegeFaculty of Science
uc.departmentSchool of Physical & Chemical Sciences
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