Don't forget the non-robot, non-Foundation short fiction. "Nightfall"' and "The Ugly Little Boy" spring to mind.
Also keep in mind before launching into reading Asimov that he was a very prolific author who pretty freelily admitted that he wrote largely to put some money in his pocket. Not that he wasn't a good writer and didn't love writing, but if he sent it out and somebody bought it, he didn't care if it was one of his BEST. The check cleared, so it was good enough. I think a lot of the Foundation stuff and Robot stuff falls into that category. It was selling, so he wrote more of it.
So, as an Asimov newbie, if you launch into trying to read things in chronological order by publication or series chronology, you may not get the best first impressions of him....
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