I'm tempted to say Hartnell. They didn't get on as well, and to a certain extent that comes across on-screen (though he was always a professional), but possibly because there's no Jamie. I love Jamie, of course, but I think the team of four leaves one of them at a loose end, and difficult to shoot.
The best Ben & Polly story is The Power of the Daleks. But Anneke Wills for me just embodies the 1960s, and Troughton barely ever visited the present day. When he did (The Faceless Ones, The Web of Fear—is that it?) there's no real stab at capturing a moment. Whereas The War Machines is a quite wonderful time capsule. That's where she shines.