Metal–organic frameworks (MOFs) have been recently
explored
as crystalline solids for conversion into amorphous phases demonstrating
non-specific mechanical, catalytic, and optical properties. The real-time
control of such structural transformations and their outcomes still
remain a challenge. Here, we use in situ high-resolution
transmission electron microscopy with 0.01 s time resolution to explore
non-thermal (electron induced) amorphization of a MOF single crystal,
followed by transformation into an amorphous nanomaterial. By comparing
a series of M-BTC (M: Fe3+, Co3+, Co2+, Ni2+, and Cu2+; BTC: 1,3,5-benzentricarboxylic acid), we demonstrate that the topology
of a metal cluster of the parent MOFs determines the rate of formation
and the chemistry of the resulting phases containing an intact ligand
and metal or metal oxide nanoparticles. Confocal Raman and photoluminescence
spectroscopies further confirm the integrity of the BTC ligand and
coordination bond breaking, while high-resolution imaging with chemical
and structural analysis over time allows for tracking the dynamics
of solid-to-solid transformations. The revealed relationship between
the initial and resulting structures and the stability of the obtained
phase and its photoluminescence over time contribute to the design
of new amorphous MOF-based optical nanomaterials.