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Polycyclic aromatic azomethine ylides (PAMYs) are powerful building blocks in the bottom-up synthesis of internally nitrogen-containing polycyclic aromatic hydrocarbons (N-PAHs) through 1,3-cycloaddition reactions. In this work, the cycloaddition reaction of PAMYs to asymmetric ortho-quinones is presented, which, in contrast to the addition to symmetric para-quinones, facilitates subsequent condensation reactions and allows the synthesis of three helical N-PAHs with ullazine-quinoxaline (UQ-1-3) backbones. UQ-1 and UQ-2 possess two helical centers; however, single-crystal X-ray analysis together with the computational modeling of UQ-3 elucidate the formation of only the thermodynamically most stable geometry with four helical centers in a (P,P,M,M) configuration. For the series UQ-1-3, the number of redox steps is directly correlated with the number of ullazine or quinoxaline units incorporated into the targeted molecular backbones. A detailed investigation of the spectroscopic and magnetic properties of the radical cation and anion as well as the dication and dianion species by in situ EPR/UV/Vis-NIR spectroelectrochemistry is provided. The excellent optical and redox properties combined with helical geometries render them possibly applicable as chiral emitter or ambipolar charge transport material in organic electronics.

Porous organic polymers (POPs) have attracted significant attention towards molecular adsorption in recent years due to their high porosity, diverse functionality and excellent chemical stability. In this work, we present a systematic case study on the formation of thiazolo[5,4-d]thiazole (TzTz) linkages through model compounds and its integration to synthesize a set of three novel, thermo-chemically stable TzTz-linked POPs, namely TzTz-POP-3, TzTz-POP-4, and TzTz-POP-5 with triphenylbenzene, tetraphenylpyrene and tetra(hydroxyphenyl)methane cores, respectively. Interestingly, the integrated TzTz moiety of the represented TzTz-POP-3 renders chemoselective removal of organic dye fluorescein (FL) from a mixture with parafuchsine (FU) in aqueous solution. The TzTz-POP-3 offered excellent chemoselectivity of ≈1:7 (FL:FU), compared to alike porous materials demonstrated for similar applications due to the presence of multiple active anchoring sites coupled with permanent porosity and appropriate pore window.

Cyano-substituted polyphenylene vinylenes (PPVs) have been the focus of research for several decades owing to their interesting optoelectronic properties and potential applications in organic electronics. With the advent of organic two-dimensional (2D) crystals, the question arose as to how the chemical and optoelectronic advantages of PPVs evolve in 2D compared with their linear counterparts. In this work, we present the efficient synthesis of two novel 2D fully sp2 -carbon-linked crystalline PPVs and investigate the essentiality of inorganic bases for their catalytic formation. Notably, among all bases screened, cesium carbonate (Cs2 CO3 ) plays a crucial role and enables reversibility in the first step with subsequent structure locking by formation of a C=C double bond to maintain crystallinity, which is supported by density functional theory (DFT) calculations. A quantifiable energy diagram of a "quasi-reversible reaction" is proposed, which allows the identification of further suitable C-C bond formation reactions for 2D polymerizations. Moreover, the narrowing of the HOMO-LUMO gap is delineated by expanding the conjugation into two dimensions. To enable environmentally benign processing, the post-modification of 2D PPVs is further performed, which renders stable dispersions in the aqueous phase.