If you want to add a foreign key to your UserProfile table, the referenced column must be a primary key or have a unique constraint.
You could manually add a unique constraint with a query like this:
ALTER TABLE tb_contacts
ADD UNIQUE (Email)
By the way, the New Relationship dialog of the WebMatrix Databases workspace displays as possible references only the tables with suitable primary keys.
Note that your StarterSite db alterations inhibit the use of the WebSecurity class.