Trying to understand why Pi-hole DHCP no longer works with my Virgin Hub 3.0.

They switched from dhcpcd to network-manager with Debian 12 (Bookwork) and up.
You can check with below two which one is enabled on your Pi:

systemctl is-enabled dhcpcd.service

systemctl is-enabled NetworkManager.service

If its Network Manager, you can configure "manual" static IP details with below one:

sudo nmtui

Example config below: