Tribenzotriquinacene-based polymers of intrinsic microporosity

Facile Assembly of Chiral Metallosquares by Using Enantiopure Tribenzotriquinacene Corner Motifs

“…The synthesis of the orthogonal bifunctional TBTQ ligand (+)‐ 1 began with the known enantiopure dihydroxy‐TBTQ derivative (−)‐ 3 (Scheme ) 12b. c O ‐Methylation of (−)‐ 3 followed by ortho ‐iodination and Sonogashira coupling with trimethylsilylacetylene (TMSA) afforded the C 1 ‐symmetric bis‐TMS‐protected acetylene (+)‐ 1 in 68 % overall yield.…”

Polymers of Intrinsic Microporosity

“…At this point, it became apparent that a wide variety of microporous organic network polymers could be prepared by the general strategy of reacting appropriate fluorinated or chlorinated monomers with complementary monomers that contain multiple catechol units (i.e., 1,2-dihydroxybenzene) such as A1. Hence, a wide range of microporous network polymers have been prepared including those containing hexaazatrinaphthylene units for efficient metal-cation binding [43], bowl shaped cyclotricatechylene [44], and tribenzotriquinacene [45] units and triptycene units that provided high and controllable surface areas (up to 1730 m 2 g −1 ) [46,47]. These networks have been studied as potential hydrogen storage materials [44,[48][49][50][51] and as heterogeneous catalysts [20,22,[52][53][54].…”

Apical Functionalization of Tribenzotriquinacenes

“…Recently, we implemented hexahydroxy TBTQs as tripodal vertices into dynamic covalent or supramolecular cage compounds. The synthesis of these outer‐rim functionalized building blocks was performed by following conventional synthetic protocols developed by other groups . In a nutshell, an acid‐catalyzed coupling of benzhydrol and indanedione derivatives leads to diketo compounds, which are ultimately transformed into TBTQs through reduction and subsequent cyclodehydration.…”

“…In this regard, both the deprotection of the methoxy groups for further functionalization at the outer rim and subsequent reactions at the apical alkyne moiety are worthwhile goals. For alkyl‐functionalized TBTQs, methoxy groups can be conveniently deprotected with BBr 3 . However, decomposition of the starting material and no product formation was observed in the case of 1 .…”

“…In the case of subphthalocyanines, functionalization at the boron center has been reported with a variety of different functional groups . For TBTQs however, besides the parent hydrocarbon, only alkyl substituents, for example, methyl, ethyl, benzyl, n‐ butyl, or iso ‐propyl, have been implemented primarily to enhance solubility in organic solvents. To facilitate further functionalization on the convex exterior of the molecular bowl, it had been stated by Kuck a decade ago, that “… in fact , introduction of a single functional group at the central carbon atom is a synthetically difficult task but an important challenge because this could offer a central point to connect larger building blocks .” However, the only example reported so far is the simultaneous introduction of amino or bromo groups at the apical and bridgehead positions .…”