If you want to use alternative bind names like the userPrincipalName (username@realm) with openLDAP, you need the rewrite/remap overlay slapo-rwm coming with version 2.4.
A very simple example would be:
# Typed and not tested!
rwm-rewriteEngine on
rwm-rewriteContext addName
rwm-rewriteRule "(.*)" "userPrincipalName=$1" ":"
rwm-rewriteMap ldap upn2dn "ldap://host/dc=my,dc=org?dn?sub"
rwm-rewriteContext bindDN
rwm-rewriteRule ".*" "${upn2dn($0)}" ":@I"
EDIT
In reply to the question in your comment: LDAP as a protocol has no concept of uniqueness, it's a product feature. With OpenLDAP for example, you can use the unique overlay to enforce uniqueness for certain attribute types in suitable backends. With phpLDAPAdmin you can configure the attribute types that shall be tested for uniqueness by that client.
username@domainas a bind name. You have to first search the directory for the user with that mail address, and use that entry's DN as the bind-name. - user207421