I have tried to export a PDF from a drawing (IDW) several times and Inventor has crashed in an uncontrolled way.
It crashed without showing any error message or even the bug typical reporting window.
Then exported to DWG and got a proper error message and no crash.
The problems seems to be connected to some write permissions to the folder where the exported files are saved to.
This could be also a problem on its own as the folder is in the active project and some other files are saved there.
I would say the error/exception handling on the code for PDF export is not as good as the one for DWG export.
By the way, never experienced anything similar until recently updated to 2021 version.
I have been able to make a PDF by printing to the Adobe PDF printer (to the same folder that was making problems with Inventor).
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