The carbazolophane (Czp) donor unit is introduced to the design pool of donors in TADF emitters.

Poly(para-xylylene)s are a unique class of chemical vapor deposition (CVD)-based polymers, generally referred to their tradename "parylenes", widely used as a protective coating and insulating layer in electronics, especially in printed circuit boards and optical and biomedical devices. Due to their unique synthesis via CVD polymerization, parylene coating conforms to a surface; however, molecularly controlled structuring of parylene particles with precise spatial arrangements over multiple hierarchical levels, tailored shapes, sizes, and porosities has not been realized. Here, we report metal−organic framework (MOF)-templated cyclophane-based CVD polymerization with morphology and porosity transcription of the host framework. This catalyst-and initiator-free template approach forms a CVD polymer in three-dimensional (3D) confined nanospaces. The paraxylene diradicals (monomers) formed during CVD polymerization using [2.2]paracyclophane (PCP) as a precursor molecule (Gorham process) diffuse into confined nanochannels of the crystalline 3D HKUST-1 MOF and spontaneously polymerize to generate parylene@MOF composites. Here, MOF confined geometries can act as a sacrificial template and, upon removal of the coordinating metal ions, facilitate the formation of templated parylene particles with the transcription of the parent crystal HKUST-1 morphology and porosity. The templated morphologies depend on subtle changes of the chemical composition of the CVD precursors as indicated by clear morphological differences observed for parylene particles synthesized from pristine and chlorosubstituted PCPs. Atomistic ab initio and classical molecular dynamics simulations and energy barrier calculations using the density functional theory−nudged elastic band method of the poly(para-xylylene) precursors in an HKUST-1 confinement were performed to study the mechanism of the molecularly controlled structuring of parylenes. The structuring process is driven by the differences in the diffusion properties of diradicals precursors inside the HKUST-1 MOF. MOF-templated CVD polymerization with implementation of 3D spatial arrangements establishes a new platform for the synthesis of functional parylene polymer particles with structurally controlled morphologies, where molecularly imprinted structuring is modulated by the choice of both the template and the CVD precursor.

A Langmuir film of cubane-bridged bisporphyrin (H 2 por-cubane-H 2 por) at the air/water interface was developed and characterized. The floating film was successfully employed for the chiral discrimination between l- and d-histidine. The enantioselective behavior persisted after the deposition of the film on a solid support using the Langmuir–Schaefer method. Distinct absorption and reflection spectra were observed in the presence of l- or d-histidine, revealing that conformational switching was governed by the interaction between H 2 por-cubane-H 2 por and the histidine enantiomer. The mechanism of chiral selection was investigated using an ad hoc modified nulling ellipsometer, indicating the anti-conformation was dominant in the presence of l-histidine, whereas the presence of d-histidine promoted the formation of tweezer conformation.

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We report a two‐step approach to obtain synthetically versatile bicyclo[1.1.1]pentane (BCP) derivatives using Grignard reagents. This method allows the incorporation of BCP units in tetrapyrrolic macrocycles and the synthesis of a new class of calix[4]pyrrole analogues by replacing two bridging methylene groups with two BCP units. In addition, a doubly N‐confused system was also formed in the presence of electron‐withdrawing substituents at the BCP bridgeheads. The pyrrole rings in BCP containing macrocycles exist in 1,3‐alternate or αβαβ conformations, as observed from single‐crystal X‐ray diffraction analyses and 2D NMR spectroscopy.