Finite-dimensional vector spaces, Paul R. Halmos, reprint of 2nd edition, paragraph 9, "Isomorphism":
Definition. Two vector spaces $\cal{U}$ and $\cal{V}$ (over the same field) are isomorphic if there is a one-to-one correspondence between the vectors $x$ of $\cal{U}$ and the vectors $y$ of $\cal{V}$, say $y = T(x)$, such that
$$ T(\alpha_1 x_1 + \alpha_2 x_2) = \alpha_1 T(x_1) + \alpha_2 T(x_2). $$
It is easy to see that isomorphic finite-dimensional vector spaces have the same dimension; to each basis in one space there corresponds a basis in the other space.
But what if I define two vector spaces $\cal{U} = \{(1, 0), \; (0, 1)\}$, and $\cal{V} = \{(1, 0, 0), \; (2, 0, 0)\}$ and a bijection $((1, 0) \mapsto (1, 0, 0), (0, 1) \mapsto (2, 0, 0))$. Then $\cal{U}$ has two elements in its basis, while $\cal{V}$ has one.
Sorry for my misconception of vector spaces. I leave it as a warning for others. In case you are interested in a very well formulated proof, read this post of bfff.
If what you mean by $\mathcal{U}$ and $\mathcal{V}$ is the vector space over $\mathbb{R}$ created by spanning off of those sets, then $\mathcal{U} = \mathbb{R}^2$ while $\mathcal{V}$ is the subspace of all elements $(x,0,0)$ in $\mathbb{R}^3$. These two vector spaces are not isomorphic: the first has dimenson $2$, the second dimension $1$.
The map $f$ you gave is therefore not capable of being an isomorphism. Suppose that $f$ was an isomorphism, so that it is linear. For one, $f(0, \frac{1}{2}) = f(\frac{1}{2}(0,1))$ is the same as $\frac{1}{2}f(0,1)=(1,0,0)=f(1,0)$ and so $f$ isn't one-to-one. So, your counterexample is not a counterexample.