Unbound times out with: "communications error to 127.0.0.1#5335: timed out"

Out of interest, on your home network try this command in a Pi-hole terminal, to check that Pi-hole can access its own service:

nslookup -class=chaos -type=txt version.bind 127.0.0.1

Try this command in the Windows terminal, to check that it can access Pi-hole's service (use the correct IP for that last part):

nslookup -class=chaos -type=txt version.bind IP_OF_PIHOLE

Both tests should give a result similar to "dnsmasq-pi-hole-v2.90+1" that makes it clear Pi-hole was queried.

Moto provided a methodical approach for testing where the failure gets introduced. You replied "Nothing happened. Thanks still, though. Was worth a try."

That response makes no sense. What will always happen is that it either all works as expected, or else it stops working as expected at some point, which is the point of using that methodical approach. So, did you go through all those steps? If so, at what exact point did you stop getting expected results? But if not, then please start over and follow it. It will allow you to identify the most likely cause. Then please report the results here.