The conversion of metal–organic frameworks (MOFs) into derivatives with a well-defined shape and composition is considered a reliable way to produce efficient catalysts and energy capacitors at the nanometer scale. Yet, approaches based on conventional melting of MOFs provide the derivatives such as amorphous carbon, metal oxides, or metallic nanoclusters with an appropriate morphology. Here ultrafast melting of MOFs is utilized by femtosecond laser pulses to produce a new generation of derivatives with complex morphology and enhanced nonlinear optical response. It is revealed that such a nonequilibrium process allows conversion of interpenetrated 3D MOFs comprising flexible ligands into well-organized spheres with a metal oxide dendrite core and amorphous organic shell. The ability to produce such derivatives with a complex morphology is directly dependent on the electronic structure, crystal density, ligand flexibility, and morphology of initial MOFs. An enhanced second harmonic generation and three-photon luminescence are also demonstrated due to the resonant interaction of 100–1000 nm spherical derivatives with light. The results obtained are in the favor of new approaches for melting special types of MOFs for nonlinear nanophotonics.@en

We demonstrate herein an all-optical switch based on stimuli-responsive and photochromic-free metal–organic framework (HKUST-1). Ultrafast near-infrared laser pulses stimulate a reversible 0.4 eV blue shift of the absorption band with up to 200 s−1 rate due to dehydration and concomitant shrinking of the structure-forming [Cu2C4O8] cages of HKUST-1. Such light-induced switching enables the remote modulation of intensities of photoluminescence of single crystals of HKUST-1 as well visible radiation passing through the crystal by 2 order of magnitude. This opens up the possibility of utilyzing stimuli-responsive MOFs for all-optical data processing devices.@en