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.
Publisher Copyright:
© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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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U2 - 10.1002/asia.202000014
DO - 10.1002/asia.202000014
M3 - Article
C2 - 32022407
AN - SCOPUS:85079458284
VL - 15
SP - 748
EP - 752
JO - Chemistry - An Asian Journal
JF - Chemistry - An Asian Journal
SN - 1861-4728
IS - 6
ER -