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

doi:10.1002/asia.202000014

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

Research output: Contribution to journal › Article › peer-review

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 language	English
Pages (from-to)	748-752
Number of pages	5
Journal	Chemistry - An Asian Journal
Volume	15
Issue number	6
DOIs	https://doi.org/10.1002/asia.202000014
Publication status	Published - Mar 16 2020

All Science Journal Classification (ASJC) codes

Biochemistry
Organic Chemistry

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@article{0dbb12e1f34c4979bd8ce24ad52d2d6b,

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

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.",

author = "Takaaki Yamamoto and Abraham, {Jibin Alex} and Shigeki Mori and Motoki Toganoh and Soji Shimizu and Masatoshi Ishida and Hiroyuki Furuta",

note = "Funding Information: The present work was supported by JSPS KAKENHI Grant Numbers (JP19H04586 and JP19K05439). Funding from the Tokuyama Research Foundation is gratefully acknowledged. T.Y. thanks JSPS for a Research Fellowship for Young Scientists. We acknowledge Prof. H. Shimakoshi at Kyushu University (Japan) for his assistance for EPR simulation.",

year = "2020",

month = mar,

day = "16",

doi = "10.1002/asia.202000014",

language = "English",

volume = "15",

pages = "748--752",

journal = "Chemistry - An Asian Journal",

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publisher = "John Wiley and Sons Ltd",

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TY - JOUR

T1 - Tungsten(VI) Complex of N-Fused Porphyrin Absorbing Near-Infrared Light beyond 1000 nm

AU - Yamamoto, Takaaki

AU - Abraham, Jibin Alex

AU - Mori, Shigeki

AU - Toganoh, Motoki

AU - Shimizu, Soji

AU - Ishida, Masatoshi

AU - Furuta, Hiroyuki

N1 - Funding Information: The present work was supported by JSPS KAKENHI Grant Numbers (JP19H04586 and JP19K05439). Funding from the Tokuyama Research Foundation is gratefully acknowledged. T.Y. thanks JSPS for a Research Fellowship for Young Scientists. We acknowledge Prof. H. Shimakoshi at Kyushu University (Japan) for his assistance for EPR simulation.

PY - 2020/3/16

Y1 - 2020/3/16

N2 - 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.

AB - 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.

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