Pi-hole's IPv6 support targets a small scenario where an IPv6-capable router would not support propagating any IPv6 DNS server at all (or only supports to disable propagation of its pre-configured IPv6 DNS servers).
In that case, enabling IPv6 support would have Pi-hole announce itself as an IPv6 DNS server.
Pi-hole's IPv6 support is not intended to replace a router's IPv6 duties (nor can it address the case where a router announces its own IPv6 address as local DNS resolver without exposing any configuration options to change or disable it).
Also, note that DHCP is strictly IPv4.
IPv6's DHCPv6 is about equivalent, but a separate protocol, and you should be carefully aware that DHCPv6 is not supported by all OSs (e.g. Android is strictly NDP/SLAAC).
IPv6 heavily emphasises auto-configuration over centrally managed network configuration.
As such, an IPv6 node would immediately construct an IPv6 link-local adress by autonomously calculating an interface identifier for a network interface and combining it with the link-local prefix - without any interaction with any router or server nodes potentially attached on the same link.
Because DHCPv6 requires a client to already have (at least) an IPv6 link-local address to communicate with the DHCPv6 server (see RFC 8415: Dynamic Host Configuration Protocol for IPv6 (DHCPv6)). So in contrast to IPv4, an IPv6 node is able to use a unicast address to communicate with a DHCPv6 server.
Because it is a router's job to advertise IPv6 prefixes - your router may just drop all packets for unknown prefixes (instead of forwarding them to public internet, which it should not do for ULA scopes).