Porous organic polymers (POPs) are chemically and thermally robust materials and have been often investigated for their gas sorption properties. From the related field of metal–organic frameworks (MOFs) it is known that open ligation sites at metal centers can enhance the performance of gas sorption significantly, especially the selectivity toward one gas of a binary mixture, such as CO2/N2 or CO2/CH4. POPs that contain metal centers are rarer. One possibility to introduce metals into POPs is by the synthesis of metal-assisted salphen organic frameworks (MaSOFs), where the framework development is associated with the formation of the metal–salphen pockets. Based on a hexakissalicylaldehyde, a variety of three-dimensional isostructural porous MaSOFs with different metal ions (Zn2+, Ni2+, Cu2+, Pd2+, and Pt2+) are introduced. All compounds show a very similar pore structure and comparable specific surface areas, which make these MaSOFs ideal candidates to study the influence of the nature of the incorporated metal center on gas sorption selectivity. Due to the environmental importance, the adsorption of CO2 in comparison to N2 and CH4 was extensively studied. Depending on the metal ions, the heat of adsorption was different as well as the Henry and IAST selectivities. Cu–MaSOF100 for instance shows a high Q st of 31.2 kJ mol–1 for CO2 and an uptake of 14.9 wt % at 1 bar and 273 K. The IAST selectivity of CO2/N2 for an 80/20 mixture is with S IAST = 52 very high for a metal containing POP and even comparable to some of the best performing MOFs. The MaSOFs are stable even in boiling water. This, as well as the simple synthesis, makes them potential good candidates for CO2 removal of binary mixtures.

A two-step method (Suzuki-Miyaura cross-coupling, followed by Scholl oxidation) to triphenylene-based triptycenes is described, rendering a variety of π-extended triptycenes accessible in high yields and without the necessity of column chromatography purification. The versatility of this reaction has been demonstrated in the synthesis of a supertriptycene in only four steps and high yields.

In 2013 the concept of OMIMs (organic molecules of intrinsic microporosity) was introduced by McKeown et al. These OMIMs are constructed on the basis of rigid molecular cores such as triptycene, spirobifluorenes, and others. Like shape-persistent organic cages, these are soluble discrete molecules and therefore an interesting alternative to 3D, insoluble porous materials, such as metal-organic frameworks, covalent-organic frameworks, or zeolites. OMIMs are chemically and thermally robust because the formation of strong covalent bonds has been used for their synthesis. To date, a few OMIMs have been reported, though most of them did not contain any functional unit to enhance gas sorption properties. This work introduces an isostructural series of metal-salphene based OMIMs with different metal ions (Zn , Ni , Cu , Pd , and Pt ) integrated into the backbone. The influence of the metal centers on interaction with gas molecules has been investigated by gas sorption experiments.

for the synthesis of para-aryl-substituted salicyldialdehydes have been reported, which would broaden the ditions, which often gave the compounds in low yields. [3] Warmuth et al., for instance, used imine condensation in a broader sense to realize shape-persistent organic cage compounds with different geometries and sizes. [4] In 2009, the group of Cooper demonstrated that [6+4] cages, synthesized by 12-fold imine condensation of 1,3,5-triformylbenzene and chiral diamines, could be freed from enclathrated solvate molecules in the crystalline state to give materials with specific surface areas of 624 m 2 g -1 , according to the Brunauer-Emmett-Teller model. [5] Since then, this new research area has been developing very quickly, [6] and besides imine condensation reactions [7][8][9] other types of reversible reactions, such as that of boronic acids and diols, have been applied to synthesize shape-persistent organic cages that can be used to create porous materials with mesopores and specific surface areas of 3758 m 2 g -1 . [10] Still, one of the most porous cages with a very high surface area of 2071 m 2 g -1 is based on the [4+6] condensation [a] 3276 Scheme 6. Imine condensation reaction of 4g and 7 to cage compound 10.www.eurjoc.org 3278 Scheme 5. Duff formylation reactions of electron-rich substituted 4-hydroxybiphenyl derivatives 5a and 5g.

A desymmetrization strategy has been developed to achieve a triptycene‐based hexamethoxy tris triphenylene in high yields by taking into account the regioselectivity of the Scholl‐type oxidative cyclodehydrogenation governed by methoxy groups. Different routes starting from D3h‐ and C3v‐symmetric precursors have been compared as well as by Mallory‐type photocyclizations.