Incorporating tungsten into the N3 core of a N-fused porphyrin (NFP; 1) affords high-valent tungsten(VI)-NFP complexes, WClO -1 and 21-chlorinated WClO -3. The X-ray structure of WClO -1 reveals a distorted octahedral geometry with sitting atop metal coordination. The absorption spectrum of WClO -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" d tungsten(VI)-NFP complexes.
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