Step 1: Expression for electric potential.
Electric potential due to a point charge is:
\[
V = \frac{kq}{r}
\]
Step 2: Same distance from centre.
All charges are placed at corners of a square, so distance of each charge from centre is same.
Thus, total potential is proportional to algebraic sum of charges.
Step 3: Write total potential.
\[
V \propto (-3Q) + (-q) + (2q) + (2Q)
\]
Step 4: Simplify expression.
\[
V \propto (-3Q + 2Q) + (-q + 2q)
\]
\[
V \propto -Q + q
\]
Step 5: Condition for zero potential.
\[
-Q + q = 0
\]
Step 6: Solve for relation.
\[
Q = q
\]
Step 7: Final conclusion.
\[
\boxed{Q = q}
\]
Hence, correct answer is option (D).