Let $v$ be an $n{\times}1$ column vector, and let $A$ be the matrix obtained from the matrix $vv^T$ by setting all diagonal entries to $0$.
Here's an answer to your first question ("When is $A$ invertible?").
If $n = 1$ then, regardless of the choice of $v$, $A$ is the $1{\times}1$ zero matrix, hence $A$ is not invertible.
Next, assume $n > 1$.
Claim: $A$ is invertible if and only if all components of $v$ are nonzero.
Justification . . .
Note that every generalized diagonal of $A$ has product equal to either $p^2$ or $-p^2$, where ${\displaystyle p = {\prod_{i=1}^n v_i}}$.
Then for each fixed $n$, there is an integer $m$, independent of $v$, such that $\text{det}(A) = mp^2$.
Claim $m \ne 0$.
Let $v$ be the $n{\times}1$ column vector with all entries equal to $1$.
For this choice of $v$, we have $p^2 = 1$, hence $\text{det}(A) = m$.
Then $A + I$ is the $n{\times}n$ matrix with all entries equal to $1$, hence
\begin{align*}
&(A + I)^2 = n(A + I)\\
\implies\; &A^2 + 2A + I = nA + nI\\
\implies\; &A^2 - (n-2)A = (n-1)I\\
\implies\; &A(A - (n-2)I)) = (n-1)I\\
\implies\; &\text{det}(A) \ne 0\\
\implies\; &m \ne 0\\
\end{align*}
Returning to the general case with $v$ unknown, then since $\text{det}(A) = mp^2$ and $m \ne 0$, it follows that $A$ is invertible if and only if all components of $v$ are nonzero, as claimed.