Tungsten(VI) Complex of N-Fused Porphyrin Absorbing Near-Infrared Light beyond 1000 nm

Takaaki Yamamoto, Jibin Alex Abraham, Shigeki Mori, Motoki Toganoh, Soji Shimizu, Masatoshi Ishida, Hiroyuki Furuta

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1 Citation (Scopus)

Abstract

Incorporating tungsten into the N3 core of a N-fused porphyrin (NFP; 1) affords high-valent tungsten(VI)-NFP complexes, WClO2-1 and 21-chlorinated WClO2-3. The X-ray structure of WClO2-1 reveals a distorted octahedral geometry with sitting atop metal coordination. The absorption spectrum of WClO2-1 displays bathochromically shifted Q-like bands beyond 1000 nm, indicating an inherently narrow HOMO-LUMO energy gap. DFT calculations show that the degeneracy of the LUMO and LUMO+1 pair of 1 is significantly resolved by the tungsten(VI) coordination. Conclusively, magnetic circular dichroism (MCD) spectroscopy and cyclic voltammetry provide a rationale for the narrow HOMO-LUMO energy gap in the “16-electron” d0 tungsten(VI)-NFP complexes.

Original languageEnglish
Pages (from-to)748-752
Number of pages5
JournalChemistry - An Asian Journal
Volume15
Issue number6
DOIs
Publication statusPublished - Mar 16 2020

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Organic Chemistry

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