I initially thought this question was about $I^2$, but I can give a definite answer for $\partial I^2$, which is that this question doesn't make sense. Note that as a topological space, $\partial I^2$ is homeomorphic to the unit circle $S^1$ (in particular, it is a topological manifold!), which can be equipped with a smooth structure in a fairly straightforward way (e.g. using the exponential map $e^{ix} : \mathbb{R} \to S^1$). So it's not clear what we would mean by the statement that $\partial I^2$ isn't smooth.
One way to make this intuition precise is to think of $\partial I^2$ as the image of $S^1$ under a continuous map $S^1 \to \mathbb{R}^2$. Then the statement you want is this: no such map can be an injective immersion. (Edit, 12/10/15: An earlier version of this answer claimed that no such map can be smooth. In fact this is false; a counterexample can be constructed by slowing down as you hit each corner using a bump function.)