In 4 dimensions it is not known whether there are any exotic smooth structures on the 4-sphere. The statement that they do not exist is known as the "smooth Poincare conjecture", and is discussed by Michael Freedman, Robert Gompf, and Scott Morrison et al. (2010) who say that it is believed to be false.
Some candidates for exotic 4-spheres are given by Gluck twists (Gluck 1962). These are constructed by cutting out a tubular neighborhood of a 2-sphere S in S4 and gluing it back in using a diffeomorphism of its boundary S2×S1. The result is always homeomorphic to S4. But in most cases it is unknown whether or not the result is diffeomorphic to S4. (If the 2-sphere is unknotted, or given by spinning a knot in the 3-sphere, then the Gluck twist is known to be diffeomorphic to S4, but there are plenty of other ways to knot a 2-sphere in S4.)
Akbulut (2009) showed that a certain family of candidates for 4-dimensional exotic spheres constructed by Cappell and Shaneson are in fact standard.
