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Inorganic–organic hybrid materials that combine both Polyoxometalates (POMs) and metal ion coordinating subunits (CSUs) represent promising multifunctional materials. Though their individual components are often biologically active, utilization of hybrid materials in bioassays significantly depends on the functionalization method and thus resulting stability of the system. Quite intriguingly, these aspects were very scarcely studied in hybrid materials based on the Wells–Dawson POM (WD POM) scaffold and remain unknown. We chose two model WD POM hybrid systems to establish how the functionalization mode (ionic vs. covalent) affects their stability in biological medium and interaction with nucleic acids. The synthetic scope and limitations of the covalent POM-terpyridine hybrids were demonstrated and compared with the ionic Complex-Decorated Surfactant Encapsulated-Clusters (CD-SECs) hybrids. The nature of POM and CSU binding can be utilized to modulate the stability of the hybrid and the extent of DNA binding. The above systems show potential to behave as model cargo-platforms for potential utilization in medicine and pharmacy. [ABSTRACT FROM AUTHOR]

Cycloplatinated complexes, with their high reactivity, combined with the capability to tailor ligands for specific catalytic processes, play a pivotal role in materials science and coordination chemistry, serving as versatile catalysts for applications in the organic synthesis of industrially relevant processes. In this report, we describe the synthesis and characterization of a new family of Pt(II) complexes based on three isomeric pyridyl‐β‐diketones diversified in terms of N‐atom location in the heterocyclic ring. By appropriate control of the reaction conditions, we were able to generate distinct coordination species, featuring ligands arranged as N,C(sp3)‐ and N,O‐chelates, as well as simple pyridyl‐N donors. Various analytical techniques, including X‐Ray diffraction, NMR spectroscopy and ESI‐MS spectrometry enabled the characterization of different coordination modes of the central atoms and unambiguously established the complex structures. Furthermore, all the Pt(II) coordination units have been found to be highly active and selective catalyst precursors in the hydrosilylation reactions within a broad scope of olefins with hydrosilanes. [ABSTRACT FROM AUTHOR]

Understanding and control of the spatiotemporal stimuli-responsiveness of flexible metal–organic frameworks are crucial for the development of novel adsorbents for gas storage and separation technologies. Herein, we report two isostructural pillared-layer dynamic frameworks differing only in one atom that bridge a benzenocarboxylate linker. Through a synthetic approach, we switch the stepwise CO2-induced transformation into a continuous one. Our findings are proved by equilibrium and time-resolved in situ powder X-ray diffraction collected during CO2 adsorption at 195 K. Finally, we use high-pressure single and multi-gas adsorption experiments to show the superiority of continuous breathing in CH4 storage and CH4/CO2 separation at 298 K. This report demonstrates that the desirable mechanism of flexible frameworks can be readily achieved through single-atom exchange enabling efficient gas separation and storage. [ABSTRACT FROM AUTHOR]

Hydrogen‐bonded polymers are a class of highly dynamic supramolecular aggregates, whose self‐assembly may be tuned by very mild external or internal stimuli. However, the rational design of chiral supramolecules remains challenging especially when flexible components are involved. The combination of the inherent weakness and dynamic nature of the intermolecular bonds that hold together such assemblies with unrestricted molecular motions introduces additional factors which may affect the self‐assembly process. In this report, the self‐assembly of four amino acid‐derived chiral biphenyldiimides into open‐chain 1D supramolecular polymers is presented. While the primary driving force, COOH···HOOC hydrogen bonding, is responsible for the polymer growth in all cases, the amino acid side chains play an important role in either stabilizing or destabilizing the assemblies obtained, as deduced from studies of the thermodynamics of the self‐assembly process. Furthermore, substantial differences in the structural factors governing the polymerization process between dynamic liquid and static solid are found. This work demonstrates the potential of the rather unexplored class of diimide‐based organic dyes in the formation of well‐organized chiral supramolecular assemblies with tunable properties. [ABSTRACT FROM AUTHOR]