Wikipedia defines a particular map between two particular objects as an unnatural isomorphism if it is an isomorphism that cannot be extended to a natural transformation on the entire category.
Dual vector spaces provide a classic example of unnatural isomorphisms. The contravariant functor sending finite dimensional vector spaces to their duals and linear maps to the adjoints cannot be naturally isomorphic to the identity, just because it is contravariant. Furthermore, as described here, one can define a form of natural transformation between covariant and contravariant functors, and the dual functor doesn't satisfy that either.
But what is wrong with the following argument. Given a particular finite-dimensional vector space $V$ and an arbitrary isomorphism $\eta_V:V\to V^*$, chose an another arbitrary isomorphism $\eta_W: W\to W^*$, for every other finite dimensional space $W\neq V$. Define a covariant functor $G$ that sends each space to its dual, and sends each map $f:W\to X$ to $G(f) = \eta_X \circ f \circ \eta_W^{-1}$. This appears to be naturally isomorphic to the identity functor, since $G(f) \circ \eta_W = \eta _X \circ f$.
The functor $G$ is certainly not the standard dual functor: it is covariant, and it does not send maps to their adjoints. However it does seem like an extension of an arbitrary map between a space and its dual, to a natural transformation on the entire category. Maybe the original definition was wrong - does it even make sense to talk about an unnatural isomorphism between a single pair of objects?
Does this mean that we cannot actually ask whether a particular map between a particular pair of objects is natural? And that naturality only makes sense as a property of an entire functor?
If so, the wikipedia article seems misleading.
– Neuromath Apr 20 '19 at 15:46