The assembly of molecular networks into structures such as random tilings and glasses has recently been demonstrated for a number of two-dimensional systems. These structures are dynamically arrested on experimental time scales, so the critical regime in their formation is that of initial growth. Here, we identify a transition from energetic to entropic stabilization in the nucleation and growth of a molecular rhombus tiling. Calculations based on a lattice-gas model show that clustering of topological defects and the formation of faceted boundaries followed by a slow relaxation to equilibrium occur under conditions of energetic stabilization. We also identify an entropically stabilized regime in which the system grows directly into an equilibrium configuration without the need for further relaxation. Our results provide a methodology for identifying equilibrium and nonequilibrium randomness in the growth of molecular tilings, and we demonstrate that equilibrium spatial statistics are compatible with exponentially slow dynamical behavior.