Host Immich on the VM. Enable NFS on the Synology, and mount the shared folder on the VM.
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So your vote is an external library
You can, or you can simply declare the network share as the library directory and it'll treat it like a regular directory.
Just use the Synology NAS as NFS share. Mount the NFS share on your server with 256GB RAM and use it as bind volume mounts for immich.
Otherwise, run immich in the server only ans properly backup all volumes to the Synology NAS regularly. Use a backup solution that notifies you if something bricks.
Would that be better than just mounting the NFS on the host and assigning that directory as the Immich upload directory?