I'm going to use the notation $<\cdot, \cdot>$ to denote the inner product.
We have a basis so each vector in the space $V$ can be expressed as a linear combination of the basis vectors $\{\alpha_{1}, \ldots , \alpha_{n}\}$.
The coordinates of a vector determine the weights to use in the linear combination.
Let $v$ be a vector with coordinates $r = (r_{1}, \ldots, r_{n})^{T} \in \mathbb{R}^{n}$, i.e. we have
$$
v = r_{1} \alpha_{1} + \ldots + r_{n} \alpha_{n}
$$
We can represent the inner products $<\alpha_{i}, v>$ using the coordinate representation of $v$ because the inner product is linear:
$$
<\alpha_{i}, v>
= r_{1} <\alpha_{i}, \alpha_{1}> + \ldots + r_{n} <\alpha_{i}, \alpha_{n}>
$$
A vector containing all the $<\alpha_{i}, v>$, for $1 \le i \le n$, can be obtained by pre-multiplying $r$ by a matrix $A$ where $A_{ij} = <\alpha_{i}, \alpha_{j}>$.
The $n\times n$ matrix $A$ is the Gramian matrix for the set of vectors $\{\alpha_{1}, \ldots, \alpha_{n}\}$. It is non-singular because the vectors in the set are linearly independent
(link)
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If we collect the values of $c_{i}$ described in the question into a vector, $c = (c_{1}, \ldots, c_{n})^{T}$,
we can ask whether we can solve uniquely for $r$ in the equation $Ar = c$. The answer is yes because $A$ is invertible.
Given that we can obtain a unique set of coordinates $r$, we can deduce that there is a unique vector in $V$ corresponding to these coordinates. This is due to the isomorphism between $V$ and the space of its coordinates $\mathbb{R}^{n}$.