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Organic-inorganic composite materials with tailored properties can be designed in the lab through bioinspired approaches.
In this context, we exploited the particle-based crystallisation process of calcium sulfate, a technologically important mineral, to hybridise inorganic and organic matter.
We identified and synthesised an organic polymer showing strong affinity to bind to the surfaces of mineral precursors as well as intrinsic tendency to self-organise. Subsequently, polymer-coated building units were allowed to self-assemble via oriented attachment, aggregation and phase transformation, which produced ordered superstructures where the organic polymer is intercalated between the subunits and surrounds the hybrid core as a shell.
This specific architecture across multiple length scales leads to unique mechanical properties, comparable to those of natural biominerals.
Thus, our results devise a straightforward pathway to prepare organic-inorganic hybrid structures via bottom-up self-assembly processes innate to the crystallisation of the inorganic phase.
This approach can likely be transferred to other inorganic minerals, affording next-generation materials for applications in the construction sector, biomedicine and beyond.
Diarylethene derivatives are photochromic molecular switches, undergoing a ring-opening/-closing reaction by illumination with light. The symmetry of the closed form is determined by the WoodWard Hoffinann rules according to which the reaction proceeds by corirotatory rotation -in that case. Here, we show by a cOrnbined approach of scanning tunneling microscopy (STM) and density functional theory (DFT) calculations that the Open isomer of 4,4'-(4,4'-(perfluorocydopent-1-ene-1,2-diyl)bis(5-methyl-thiophent-4,2,4-dipyridine) (PDTE) retains its open form upon adsorption on a Ag(111) surface. It caribe switched into a closed form, which we identify as the digrotatOly cydization product, by controlled manipulation 'With the STM tip, Evidence of an electric-field dependent switching-process 'is interpreted on the basis of a Simple electroStatic Model, which suggests that the reaction proceedS via an "upright" intermediate state. This pathway thus strongly differs from the switching reaction in solution.