Discrete Triptycene‐Based Hexakis(metalsalphens): Extrinsic Soluble Porous Molecules of Isostructural Constitution

Abstract

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.

Triptycene End‐Capped Quinoxalinophenanthrophenazines (QPPs): Influence of Substituents and Conditions on Aggregation in the Solid State

“…As an example, sublimated thin films of pentacene typicallyc onsist of two different crystallographic phases. [28] During our work on triptycene-based organic molecules of intrinsicm icroporosity (OMIMs), [29][30][31][32][33] we observed the formation of hexagonal arrangements of these molecules by ar elatively tight p stacking of the large aromatic quinoxalinophenanthrophenazine (QPP) planes, despite the existing tert-butyl groups at the pyrene units. [26,27] Very recently,o ne-dimensionalm ixed stacks of acene and azaacene derivatives with a high structuralo verlap of the p planes through an hydrogenbonding-assisted encapsulatingapproach, which shouldbeoptimal for charge transport,have been reported.…”

“…[26,27] Very recently,o ne-dimensionalm ixed stacks of acene and azaacene derivatives with a high structuralo verlap of the p planes through an hydrogenbonding-assisted encapsulatingapproach, which shouldbeoptimal for charge transport,have been reported. [28] During our work on triptycene-based organic molecules of intrinsicm icroporosity (OMIMs), [29][30][31][32][33] we observed the formation of hexagonal arrangements of these molecules by ar elatively tight p stacking of the large aromatic quinoxalinophenanthrophenazine (QPP) planes, despite the existing tert-butyl groups at the pyrene units. [34] Fascinated by this structural motif, four structurally related QPP model compounds were synthesized, and the influence of tert-butyl groups and the triptycene endcaps weres tudied experimentally and theoretically (Figure1).…”

Microporous Triptycene‐Based Affinity Materials on Quartz Crystal Microbalances for Tracing of Illicit Compounds

“…In particular, triptycene derived OMIM exhibit high specific surface areas of up to 754 m 2 g À 1 , making them excellent materials for gas sorption. [18][19][20][21][22] Up to now, OMIMs have not been tested as affinity materials for QCMs. Because of their microporosity and rigidity, this type of affinity material could be beneficial for QCM-based sensing.…”

Triptycene-Based and Amine-Linked Nanoporous Networks for Efficient CO2 Capture and Separation

“…The H 2 uptake by TBPALs was found to be in the range of 11.4-16.2 mg/g ( Table 2 and Figure 6). The highest value was obtained for TBPAL2 (16.2 mg/g), and this is better than various MOPs and MOFs such as azo-bridged porphyrin-based conjugated microporous polymers (8.6-11.5 mg/g) (Xu et al, 2016b), triptycene-based hexakis (metalsalphens) (6-7 mg/g) (Reinhard et al, 2018), 3D ultramicroporous triptycene-based polyimide framework (14.1 mg/g) (Ghanem et al, 2016), rigid triptycene-hexaacid H 6 THA (7.8-11.8 mg/g) (Chandrasekhar et al, 2017a), porous hydrogenbonded MOFs (1.1-1.3 mg/g) (Chandrasekhar et al, 2017b), carbazole-based POPs (11.9-12.9 mg/g) (Zhu et al, 2014), and phthalocyanine-based porous polymer (9 mg/g). (Neti et al, 2015) From the above comparison, it is clear that TBPALs reported herein show H 2 uptake abilities that are better than several microporous polymeric networks reported previously in the literature.…”

“…According to IUPAC, "the type H4 loop appears to be associated with narrow slit-like pores" (Sing, 1982). A MOPs such as triptycene-based polymeric nanosheet (2D-PTNS) (690 m 2 g −1 ) (Chen et al, 2017), triptycene-based hexakis (metalsalphens) (356-427 m 2 g −1 ) (Reinhard et al, 2018), and BODIPY-containing POPs (482-725 m 2 g −1 ) (Xu et al, 2016a). Pore dimensions of TBPALs were estimated using the N 2 sorption isotherms and by using the density functional theory (DFT) method.…”