4.8 Article

Photoactive ultrathin molecular nanosheets with reversible lanthanide binding terpyridine centers

Journal

NANOSCALE
Volume 13, Issue 48, Pages 20583-20591

Publisher

ROYAL SOC CHEMISTRY
DOI: 10.1039/d1nr05430a

Keywords

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Funding

  1. Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) [INST 275/257-1 FUGG, TU149/5-1, TU149/8-2, TRR 234, 364549901]
  2. ESF [2020 FGR 0051]
  3. German Research Council (DFG)
  4. Deutscher Akademischer Austauschdienst (DAAD) [075-03-2021-094/4 (2331-21)]
  5. Russian Federal Ministry for Education and Science [075-03-2021-094/4 (2331-21)]

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This study presents a method for synthesizing photoactive metal-organic nanosheets with ultimate molecular thickness and the ability to reversibly complex lanthanide ions. These nanosheets can be prepared on a large scale, possess mechanical stability as free-standing sheets, and exhibit photoactivity inherited from the pristine terpyridine lanthanide complex. They offer a simple and robust way for preparing ultrathin nanosheets with tailored photoactive properties for applications in photocatalytic and energy conversion devices.
In recent years, functional molecular nanosheets have attracted much attention in the fields of sensors and energy storage. Here, we present an approach for the synthesis of photoactive metal-organic nanosheets with ultimate molecular thickness. To this end, we apply low-energy electron irradiation induced cross-linking of 4 '-(2,2 ':6 ',2 ''-terpyridine-4 '-yl)-1,1 '-biphenyl-4-thiol self-assembled monolayers on gold to convert them into functional similar to 1 nm thick carbon nanomembranes possessing the ability to reversibly complex lanthanide ions (Ln-CNMs). The obtained Ln-CNMs can be prepared on a large-scale (>10 cm(2)) and inherit the photoactivity of the pristine terpyridine lanthanide complex (Ln(iii)-tpy). Moreover, they possess mechanical stability as free-standing sheets over micrometer sized openings. The presented methodology paves a simple and robust way for the preparation of ultrathin nanosheets with tailored photoactive properties for application in photocatalytic and energy conversion devices.

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