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Path adjustment in FileWrite1-3 in launcher ini, ForwardSlash should be used.
IMO working directory should be set to the database directory i.e. %Portableapps.comDocuments% as the app open the working directory when we create a new database in first run.
This is a bug in KeePassXC itself. The local version similarly tries to create a database in your Program Files by default, which would fail on anything newer than Windows XP. Setting a working directory could be a bad idea as it could break other components if DLLs aren't relative to where they're expecting. A local install has the shortcut set with a working directory of the path containing KeePassXC.exe. It's worth noting that there's a big directory you see as soon as you click New that says "_==Do Not Create Databases Here!==" and the installer is configured to preserve any KDBX files that a user accidentally saves there just to be safe.
This is also a separate issue from the bug reported above.
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This is fixed in 2.2.0 Rev 2