I haven't worked for one but I did a project with one in biz school and a project with another founded by an employee of a Top 100. The only reason I didn't go to work for one (I really wanted to work for a Black owned business) was that there weren't any on that list in the industry I wanted at the time (manufacturing except auto).
Are you interested in working or an internship?
If you have an industry or even just a position you are interested in, it is a good idea to consider a BE 100 or another Black owned business who will at least make sure your talents enrich the community.