3 years ago

Through-Space or Through-Bond? The Important Role of Cofaciality in Orbital Reordering and Its Implications for Hole (De)stabilization in Polychromophoric Assemblies

Through-Space or Through-Bond? The Important Role of Cofaciality in Orbital Reordering and Its Implications for Hole (De)stabilization in Polychromophoric Assemblies
Rajendra Rathore, Denan Wang, Shriya H. Wadumethrige, Maxim V. Ivanov
Developing predictive tools for the elucidation of redox and optical properties of polychromophoric assemblies is crucial for the rational design of efficient charge-transfer materials. Here, such tools are introduced to explain the curious observation that a pair of bichromophoric electron donors based on ethanoanthracene (5) and dihydroanthracene (DHA or 11), having similar interchromophoric separation between the carbons in the region of orbital overlap, show dramatically different (>300 mV) stabilization of their cation radicals. Analysis of molecular orbital diagrams reveals the important interplay between through-space and through-bond electronic couplings, which results in HOMO/HOMO–1 swapping in 11 (HOMO = highest occupied molecular orbital). Unlike the antisymmetric singly occupied molecular orbital (SOMO) that stabilizes a hole by charge resonance in 5•+ (0.57 V), the symmetric SOMO in 11•+ (0.88 V) does not afford hole stabilization by charge resonance; rather, the hole localizes onto a single benzenoid unit. This important finding is expected to aid in the design of polychromophoric assemblies with chromophores of graded redox potentials for optimization of long-range charge transfer.

Publisher URL: http://dx.doi.org/10.1021/acs.jpcc.7b05804

DOI: 10.1021/acs.jpcc.7b05804

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.