Control of Dynamic sp3-C Stereochemistry

Stereogenic sp3-hybridized carbon centres are fundamental building blocks of chiral molecules. Unlike dynamic stereogenic motifs, such as sp3-nitrogen centres or atropisomeric biaryls, sp3-carbon centres are usually fixed, requiring intermolecular reactions to undergo configurational change. Here, we report the internal enantiomerization of fluxional carbon cages and the consequences of their adaptive configurations for the transmission of stereochemical information. The sp3-carbon stereochemistry of the rigid tricyclic cages is inverted through strain-assisted Cope rearrangements, emulating the low-barrier configurational dynamics typical for sp3 nitrogen inversion or conformational isomerism. This dynamic enantiomerization can be stopped, restarted, or slowed by external reagents, while the configuration of the cage is controlled by neighbouring, fixed stereogenic centres. As part of a phosphoramidite–olefin ligand, the fluxional cage acts as a conduit to transmit stereochemical information from the ligand while also transferring its dynamic properties to chiral-at-metal coordination environments, influencing catalysis and ligand exchange energetics.

Unraveling the Guest-Induced Switchability in the Metal-Organic Framework DUT-13(Zn)

A guest-induced flexibility in the framework DUT-13 was investigated in situ to analyze the breathing mechanism upon physisorption of nitrogen (77 K) and n-butane (273 K). The crystal structure of cp phase, solved from PXRD data using the computation-assisted semiempirical approach, shows two times smaller pore volume, compared to the op phase, which is consistent with the corresponding isotherms. The contraction mechanism is mainly based on the conformational isomerism of the benztb4- linker, which transforms from a staggered conformation in op phase to a more eclipsed in cp phase, leading to the contraction of the larger pore. A nearly complete op → cp → op transition was observed in the case of n-butane adsorption at 273 K, while in case of weakly interacting nitrogen molecules a portion of the sample remains in the op phase in the entire pressure range. Apparently, in case of DUT-13 the contraction is crystallite size-dependent, similarly as in a number of other switchable MOFs, which should be investigated more in detail in the future. Methane adsorption at varying temperatures showed a wide hysteresis at the temperatures between 111 K and 140 K. The hysteresis width decreases until it disappears completely at 170 K leading to a reversible isotherm, typical for rigid frameworks. The fact that breathing is observed in a broader temperature range in comparison to DUT‑49 demonstrates that thermodynamics and kinetics favour the DUT-13 contraction. Linker and hinges in DUT-13 are not stiff enough to support the metastable states required for NGA.

Unraveling the Guest-Induced Switchability in the Metal-Organic Framework DUT-13(Zn)

A guest-induced flexibility in the framework DUT-13 was investigated in situ to analyze the breathing mechanism upon physisorption of nitrogen (77 K) and n-butane (273 K). The crystal structure of cp phase, solved from PXRD data using the computation-assisted semiempirical approach, shows two times smaller pore volume, compared to the op phase, which is consistent with the corresponding isotherms. The contraction mechanism is mainly based on the conformational isomerism of the benztb4- linker, which transforms from a staggered conformation in op phase to a more eclipsed in cp phase, leading to the contraction of the larger pore. A nearly complete op → cp → op transition was observed in the case of n-butane adsorption at 273 K, while in case of weakly interacting nitrogen molecules a portion of the sample remains in the op phase in the entire pressure range. Apparently, in case of DUT-13 the contraction is crystallite size-dependent, similarly as in a number of other switchable MOFs, which should be investigated more in detail in the future. Methane adsorption at varying temperatures showed a wide hysteresis at the temperatures between 111 K and 140 K. The hysteresis width decreases until it disappears completely at 170 K leading to a reversible isotherm, typical for rigid frameworks. The fact that breathing is observed in a broader temperature range in comparison to DUT‑49 demonstrates that thermodynamics and kinetics favour the DUT-13 contraction. Linker and hinges in DUT-13 are not stiff enough to support the metastable states required for NGA.

Conformational isomerism involving carboxylate groups of a linker in metal organic frameworks and its distinctive influence on the detection of ketones

In this work, the influence of solvent and reaction conditions (solvothermal vs room temperature) on the product formation is analyzed with two Zn(II) MOFs, {[Zn(bpaipa)]·DMF·2H2O}n (1) and {[Zn(bpaipa)]·5H2O}n (2), where...

Isomeric anthracene diimide polymers

Two anthracene diimide (ADI) polymers with the backbone conformational isomerism, new members of aromatic diimide polymers family, have been synthesized as a class of highly promising n-type semiconductors for organic electronics.

Distance makes a difference in crystalline photoluminescence

Crystallization-induced photoluminescence weakening was recently revealed in ultrasmall metal nanoparticles. However, the fundamentals of the phenomenon are not understood yet. By obtaining conformational isomer crystals of gold nanoclusters, we investigate crystallization-induced photoluminescence weakening and reveal that the shortening of interparticle distance decreases photoluminescence, which is further supported by high-pressure photoluminescence experiments. To interpret this, we propose a distance-dependent non-radiative transfer model of excitation electrons and support it with additional theoretical and experimental results. This model can also explain both aggregation-induced quenching and aggregation-induced emission phenomena. This work improves our understanding of aggregated-state photoluminescence, contributes to the concept of conformational isomerism in nanoclusters, and demonstrates the utility of high pressure studies in nanochemistry.