I always assumed the !
just indicated that the hash fragment that followed corresponded to a URL, with !
taking the place of the site root or domain. It could be anything, in theory, but it seems the Google AJAX Crawling API likes it this way.
The hash, of course, just indicates that no real page reload is occurring, so yes, it’s for AJAX purposes. Edit: Raganwald does a lovely job explaining this in more detail.