Interactions between dehydrobenzo[12]annulene (DBA) and gas molecules: do the preorganized acetylenes work cooperatively?

Abstract

Intermolecular interactions of the cyclic conjugated molecule (DBA) with hydrogen, nitrogen and carbon dioxide molecules were evaluated by high level ab initio calculations.

A C3‐Symmetric Macrocycle‐Based, Hydrogen‐Bonded, Multiporous Hexagonal Network as a Motif of Porous Molecular Crystals

“…On the other hand, crystallization of 1 in the presence of aromatic additives gave low-density H-HexNets. DBA 1 dissolved in a mixture of DMF and methyl benzoate (MeBz) at 50 8C yielded 1-2D1(MeBz) crystals [14] are accommodated in the unit cell with a host/guest ratio of 1:6 ( Figures S8, S16, and S20). The H-HexNet was stacked without interpenetration to give a 3D framework (Figure 4 b).…”

“…Crystallization from a DMF solution yielded 1-1D ( Figure S7), [14] in which DMF molecules are bonded through hydrogen bonds with four carboxy groups of 1 to prevent the H-HexNet structure. On the other hand, crystallization of 1 in the presence of aromatic additives gave low-density H-HexNets.…”

“…Preliminary, to confirm whether PhT is a robust supramolecular motif in a solid state, reference compounds 2 a, 2 b, and 3 (Figure 2 a) were crystallized from a solution of DMF, 1,2,4-trichlorobenzene (124TCB), and 1,3,5-trichlorobenzene (135TCB) at 50 8C. [14] X-ray crystallographic analysis of the obtained single crystals revealed that, although 2 a formed an infinite zigzag strand ( Figure S1), 2 b achieved the PhT through hydrogen-bonded dimerization of the carboxy groups (Figure 2 b). The PhT possesses a triangular void with 12.5 on a side and a diameter of 9.7 .…”

“…Subsequently, 1 was crystallized under various conditions (Scheme 1) to construct a 3D assembly of H-HexNet, yielding three types of crystals (1-1D, 1-2D1, and 1-2D2). Crystallization from a DMF solution yielded 1-1D ( Figure S7), [14] in which DMF molecules are bonded through hydrogen bonds with four carboxy groups of 1 to prevent the H-HexNet structure. On the other hand, crystallization of 1 in the presence of aromatic additives gave low-density H-HexNets.…”

“…On the other hand, crystallization of 1 in the presence of aromatic additives gave low-density H-HexNets. DBA 1 dissolved in a mixture of DMF and methyl benzoate (MeBz) at 50 8C yielded 1-2D1(MeBz) crystals [14] (Figures 3 a and 4a-d). The 1-2D1(MeBz) crystal involves the PhT motif (Figure 3 a), in which one pair of the hydrogen-bonded carboxy phenyl groups shows conformational frustration.…”