Interesting on the switch from the Windows/MS stack. Is there not a decent No SQL option for a windows stack?
Also, what would a No SQL data store give them (for central data storage - not caching) that they aren't already handling with SQL? Keep in mind that they also have relatively easily partionable data (if necessary they can break off any StackExchange site and database to their own dedicated hardware).
I was looking for something like this a while ago for my startup but we ended up going with Azure and using their Table Storage.
I'm guessing they didn't want to use a technology that is so recently out of beta perhaps?