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The ability of a compound to broadly absorb light across the incident solar spectrum is an important design target in the development of molecular photosensitizers. The 'HOMO inversion' model predicts that for [(tpy)2Fe]2+ (tpy = 2,2'6',2″-terpyridine) compounds, adjusting the character of the highest occupied molecular orbital (HOMO) from metal-centered to ligand-centered can drastically improve photophysical properties by broadening absorption in the visible and increasing molar extinction coefficients. In an effort to experimentally re