OpenType question: sub missing characters

Hi! I’m wondering whether it is possible with OpenType to catch unicode characters that are NOT in the font and replace them with something from the font?
For instance, some fonts keep hardcoded or ligatures for compatibility reasons only, even though there’s no design need for them. Wouldn’t it be better to catch them on a feature level and replace by f and i or l without maintaining the extra ligature glyphs? Does OpenType allow that?

No, but you can include an empty ligature glyph and decompose that one (preferably with the ccmp feature).

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