I do not understand your question.
I think I know what an unassigned spectrum is in DDA data, but that definition doesn't really apply to DIA spectra.
If you want to export lists of numbers from Skyline, the way to do that is by creating a custom report which you can learn about in the Custom Reports tutorial:
https://skyline.ms/wiki/home/software/Skyline/page.view?name=tutorial_custom_reports
However, custom reports cannot be used to export spectra.
Can you clarify what you are asking?
-- Nick