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Donaldson (1983) showed there exists an exotic smooth Differential Structure on 
.  Donaldson's result has
been extended to there being precisely a Continuum of nondiffeomorphic Differential Structures on 
.
See also Exotic Sphere
References
Donaldson, S. K.  ``Self-Dual Connections and the Topology of Smooth 4-Manifold.''  Bull. Amer. Math. Soc. 8, 81-83, 1983.
 
Monastyrsky, M.  Modern Mathematics in the Light of the Fields Medals.  Wellesley, MA: A. K. Peters, 1997.