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. 2018 Jul 20;24(41):10550-10556.
doi: 10.1002/chem.201802356. Epub 2018 Jun 27.

Quantitative and Orthogonal Formation and Reactivity of SuFEx Platforms

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Free PMC article

Quantitative and Orthogonal Formation and Reactivity of SuFEx Platforms

Digvijay Gahtory et al. Chemistry. .
Free PMC article

Abstract

The constraints of minute reactant amounts and the impossibility to remove any undesired surface-bound products during monolayer functionalization of a surface necessitate the selection of efficient, modular and orthogonal reactions that lead to quantitative conversions. Herein, we explore the character of sulfur-fluoride exchange (SuFEx) reactions on a surface, and explore the applicability for quantitative and orthogonal surface functionalization. To this end, we demonstrate the use of ethenesulfonyl fluoride (ESF) as an efficient SuFEx linker for creating "SuFEx-able" monolayer surfaces, enabling three distinct approaches to utilize SuFEx chemistry on a surface. The first approach relies on a di-SuFEx loading allowing dual functionalization with a nucleophile, while the two latter approaches focus on dual (CuAAC-SuFEx/SPOCQ-SuFEx) click platforms. The resultant strategies allow facile attachment of two different substrates sequentially on the same platform. Along the way we also demonstrate the Michael addition of ethenesulfonyl fluoride to be a quantitative surface-bound reaction, indicating significant promise in materials science for this reaction.

Keywords: click chemistry; fluorine; sulfur; surface chemistry; surface modification.

Figures

Scheme 1
Scheme 1
a) Surface‐bound SuFEx reaction with amines. b) Multiple or sequential orthogonal interfacial SuFEx click reactions as used in this study.
Figure 1
Figure 1
Fragments obtained in negative (blue) and positive (red) ion mode upon DART analysis of a selection of SuFEx products indicating cleavage of a S−N or S−OAr bond.
Scheme 2
Scheme 2
General scheme showing the design of the interfacial SuFEx, CuAAC and SPOCQ reactions under study.
Figure 2
Figure 2
a) Stacked XPS wide spectra of M2M11 surfaces. b) Stacked F1s narrow spectra for M2 and M3 surfaces showing the disappearance of F1s peak upon complete reaction. c) Stacked Br3d narrow spectra for the M4 and M5 surfaces showing the disappearance of the Br3d signal upon complete propargylation. d) Schematic impression of the S−N bond fragmentation and subsequent ionization of protonated 4‐iodobenzylamine (m/z 233.9774) by DART‐HRMS.
Scheme 3
Scheme 3
Surface M9 might undergo equilibration with aziridine surface M13, although the Michael addition and subsequently the SPOCQ reaction will pull the equilibrium to the left.
Figure 3
Figure 3
a) General schematic showing SuFEx reaction on M8 surfaces by microcontact (μCP) stamping with aminoferrocene. b) SEM image obtained for M12 surfaces after μCP showing the 5 μm patterns (scale=100 μm). c) XPS wide spectrum for M12 surfaces showing the Fe2p signal (inset: Fe2p narrow scan).
Figure 4
Figure 4
a) Schematic depiction of SuFEx reaction using IBZ on M2, and b) normalized DART‐HRMS intensity versus time (min) for di‐SuFEx (M2 to M3) Inserts: Linear plots of ln [(I I t)/(I I 0)] versus time (min) to obtain the pseudo‐first order constants.

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