3 years ago

Recognizing Through-Bond and Through-Space Self-Exchange Charge/Spin Transfer Pathways in Bis(triarylamine) Radical Cations with Similar Geometrical Arrangements

Tatsuya Kazama, Masashi Uebe, Ryohei Kurata, Akihiro Ito, Daisuke Sakamaki
Radical cations of bis(triarylamine)s, 3 and 4, in which the triarylamine redox centers are bridged by ortho-phenylene and ortho-carborane cluster, respectively, have been prepared to elucidate the difference in intramolecular charge/spin transfer (ICT/IST) pathway due to the two different bridging units affording similar geometrical arrangements between the redox centers. Electrochemistry, absorption spectroscopy, VT-ESR spectroscopy, and DFT calculations reveal that 3*+ and 4*+ are classified into class-II and class-I mixed valence systems, respectively, and therefore, through-bond and through-space mechanisms are dominant for the ICT/IST phenomena in 3*+ and 4*+, respectively. Moreover, SQUID measurements for dicationic species provides the fact that virtually no spin-exchange interaction is observed for 42+, while the intramolecular antiferromagnetic coupling between spins in 32+, in accordance with the existence of conjugation pathway for ortho-phenylene bridge.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/anie.201709874

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.