I set up a Debian Bookworm VM and was able to build Sigil and PageEdit with Qt6 (from the current github instructions), but I couldn't replicate your problem launching PageEdit from Sigil with the Launch External Xhtml Editor button. I used the the preferences to browse to /usr/local/bin/pageedit and selected it as by external xhtml editor and it launched from the menu button just fine (and from the F2 keyboard shortcut as well).
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