3 years ago

Diferrocenes Bridged by a Geminal Diethynylethene Scaffold with Varying Pendant Substituents: Electronic Interactions in Cross-Conjugated System

Diferrocenes Bridged by a Geminal Diethynylethene Scaffold with Varying Pendant Substituents: Electronic Interactions in Cross-Conjugated System
Ke-Ke Cao, Ying-Le Pan, Hua-Min Li, Hai-Ting Lu, Xu Zhang, Yang Fan, Meng-Li Zhang, Pei-Lin Ma, Guo-Dong Zou
A series of geminal diethynylethene (gem-DEE) bridged diferrocenyl compounds with varying pendant substituents at the side chain, including xanthene, thioxanthene, dibenzo[a,d]cycloheptene, and fluorene, is reported with the aim of exploring electronic interactions in the cross-conjugated system. The compounds 9-[bis(ferrocenylethynyl)methylene]-9H-xanthene (1), 9-[bis(ferrocenylethynyl)methylene]-9H-thioxanthene (2), 5-[bis(ferrocenylethynyl)methylene]-5H-dibenzo[a,d]cycloheptene (3), and 9-[bis(ferrocenylethynyl)methylene]-9H-fluorene (4) were synthesized and characterized by using spectroscopic methods and single-crystal X-ray diffraction analyses. Electrochemical measurements using the weakly coordinating electrolyte Na[B{C6H3(3,5-CF3)2}4] reveal the moderate electronic coupling between the ferrocenyl (Fc) termini. Hush analysis of the intervalence charge-transfer (IVCT) bands for the monocation species is suggestive of the weakly coupled Robin–Day class II mixed-valence compounds. DFT and TDDFT calculations suggest that the low-energy transitions of these compounds mainly involve a metal to ligand charge transfer (MLCT) transition from the iron center of ferrocenyl termini to the pendant substituent.

Publisher URL: http://dx.doi.org/10.1021/acs.organomet.7b00686

DOI: 10.1021/acs.organomet.7b00686

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.