Organometallics
Organometallics
5 years ago

Synthesis, Structures, and Redox Properties of Tetracyano-Bridged Diferrocene Donor–Acceptor–Donor Systems

Synthesis, Structures, and Redox Properties of Tetracyano-Bridged Diferrocene Donor–Acceptor–Donor Systems
Victor N. Nemykin, Dustin Nevonen, Ellen M. Monzo, Thaksen Jadhav, Shaikh M. Mobin, Rajneesh Misra
A set of tetracyanobutadiene (TCBD)- and dicyanoquinodimethane (DCNQ)-bridged ferrocenyl dimers 5–8 were designed and synthesized by the [2 + 2] cycloaddition–retroelectrocyclization reaction of diferrocenyl complexes 3 and 4 with tetracyanoethylene (TCNE) and 7,7,8,8 tetracyanoquinodimethane (TCNQ), respectively. The effect of constitutional isomers (para vs meta) and different acceptors on their donor–acceptor interactions and photophysical and redox properties as well as electronic structures was evaluated using a variety of experimental and theoretical methods. The single-crystal X-ray structures of TCBD- and DCNQ-bridged ferrocenyl dimers 6 and 7 are reported. The DCNQ-bridged ferrocenyl dimers 7 and 8 have lower HOMO–LUMO gap values with red-shifted absorption bands in comparison to those of TCBD-bridged ferrocenyl dimers 5 and 6. Mössbauer spectra of 3–8 are suggestive of very similar isomer shifts and quadrupole splittings in all diferrocene complexes despite their different proximities to the electron-withdrawing fragment. Spectroelectrochemical data on 5–8 are suggestive of the presence of ferrocene-centered HOMOs in these compounds as well as a lack of electronic coupling between ferrocene groups.

Publisher URL: http://dx.doi.org/10.1021/acs.organomet.7b00728

DOI: 10.1021/acs.organomet.7b00728

You might also like
Discover & Discuss Important Research

Keeping up-to-date with research can feel impossible, with papers being published faster than you'll ever be able to read them. That's where Researcher comes in: we're simplifying discovery and making important discussions happen. With over 19,000 sources, including peer-reviewed journals, preprints, blogs, universities, podcasts and Live events across 10 research areas, you'll never miss what's important to you. It's like social media, but better. Oh, and we should mention - it's free.

  • Download from Google Play
  • Download from App Store
  • Download from AppInChina

Researcher displays publicly available abstracts and doesn’t host any full article content. If the content is open access, we will direct clicks from the abstracts to the publisher website and display the PDF copy on our platform. Clicks to view the full text will be directed to the publisher website, where only users with subscriptions or access through their institution are able to view the full article.