The reaction medium and conditions are the key parameters defining the efficiency and performance of a homogeneous catalyst. In the state-of-the-art molecular descriptions of catalytic systems by density functional theory (DFT) calculations, the reaction medium is commonly reduced to an infinitely diluted ideal solution model. In this work, we carry out a detailed operando computational modeling analysis of the condition dependencies and nonideal solution effects on the mechanism and kinetics of a model ester hydrogenation reaction by a homogeneous Mn(I)-P,N catalyst. By combining DFT calculations, COSMO-RS solvent model, and the microkinetic modeling approach, the kinetic behavior of the multicomponent homogeneous catalyst system under realistic reaction conditions was investigated in detail. The effects of the reaction medium and its dynamic evolution in the course of the reaction were analyzed by comparing the results obtained for the model methyl acetate hydrogenation reaction in a THF solution and under solvent-free neat reaction conditions. The dynamic representations of the reaction medium give rise to strongly nonlinear effects in the kinetic models. The nonideal representation of the reaction medium results in pronounced condition dependencies of the computed energetics of the elementary reaction steps and the computed kinetic profiles but affects only slightly such experimentally accessible kinetic descriptors as the apparent activation energy and the degree of rate control.

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.

Photoluminescent compounds can undergo various structural changes upon interaction with light. When these changes manifest themselves in the excited state, the resulting emitters can obtain a sensory function. In this work, we designed coordination compounds that can vary their emission color in response to thermal and mechanical stimuli. When embedded in a polymer matrix, Cu-NHC sensors act as mechanophores, and their color-based response can readily describe mechanical stress and phase transition phenomena. A strong practical advantage of new mechanophores over previous generations of organometallic stress sensors stems from their reliance on emission color variations that are easy to detect. In a broad context, our work implies that emission color variations that we often view as thermally governed can also be triggered mechanically and used to generate sensory information.

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.