Cyclotricatechylene

Cyclotriveratrylene/1180-60-5] (34) is a cyclocondensation product of veratrole with formaldehyde. It possesses a stable trigonal crown conformation and forms crystalline inclusion compounds with benzene, chlorobenzene, toluene, thiophene, decalin, chloroform, acetone, carbon disulfide, acetic acid, and butyric acid (101). Their structures consist of columns of cyclotriveratrylene molecules that are not amenable to close packing and provide channels into which the guests are accommodated. A number of modified host structures, derived from prototype (34) have been prepared. The hexaphenol analogue cyclotricatechylene also yields well-defined channel inclusions (101). They involve mosdy polar guests and the structures are held by hydrogen bonding. 

Cyclotriveratrylene (1) and its hexademethylated derivative cyclotricatechylene (16) (Table 2) form crystalline inclusion compounds with a great variety of small to medium-sized molecules. These inclusion compounds have been described in a previous review [9] and will not be further considered here. 

Fig. 6.1.4. (a) Cyclotricatechylene hexaesters, the cores of which are cone-shaped (Malthete and Collet ), (b) hexa-(p-n-dodecyloxybenzoyl) derivative of macro-cyclic polyamines which is hollow at the centre (Lehn, Malthete and Levelut ). Both (a) and (b) show columnar mesophases the latter mesophase has been... 

Columnar mesophases are also formed when the flat core of the molecule is replaced by a conical one as in the cyclotricatechylene hexaesters (fig. 6.1.4(a)). With macrocyclic molecules, which are hollow at the centre (fig. 6.1.4(A)), the columns are in the form of tubes these mesophases have been described as tubular . ... 

The typical examples of macrocyclic cyclophanes, e.g., cyclotriver-atrylene, cyclotricatechylene, or tri-O-thymotide, form clathrate compounds. Significant host-host interaction affords a cage or a channel between the host molecules for guest accomodation in these lattice (cavity) inclusion crystals, (Host) (Guest). ... 

Similarly, 6°-metacyclophane forms clathrate complexes with benzene derivatives or alicyclic compounds, where only a little guest selectivity has been found ) The ratio n/m of these crystal lattice (cavity) inclusion compounds varies significantly, e.g., n/m=0.3-0.6 (cyclotricatechylene), 2-6 (tri-O-thymotide). It has been found that tri-O-thymotide resolves optical isomers, e.g., 2-butyl halides, by making host-guest inclusion crystals. These optical resolutions are therefore attributable to the crystal lattice chirality that was induced... 

By introducing undulated macrocyclic cyclotricatechylene (CTC) into 2D COFs, Zheng and co-workers found that the storage capacity of Ha can be increased. The obtained CTC-COF shows a higher Ha uptake of 1.12 wt% at 1.05 bar than those of similar 2D COFs, and even close to those of 3D COFs. Mendoza-Cortes et al. found theoretically that the total Ha uptake of COF-301-PdCla reaches 60 g L at 100 bar, which is much higher than the DOE 2015 target (40 g L ). ... 

A special kind of PIM network has been demonstrated to adsorb around 1.5-1.7 wt% H2 at 77.3 K and 1 bar, and up to 2.71 wt% at 10 bar. Hydrogen uptake for these materials is observed to be 1.4% by mass adsorbed at 1 bar and 1.7% at 10 bar for the cyclotricatechylene-PIM (CTC-PIM). The tripty-cene-based polymer (Trip-PIM) shows a better result of 1.6% by mass at 1 bar and 2.7% at 10 bar. Porphyrin-PIM (Porph-PIM) and PIM-7 have also been reported to absorb significant amounts of Ha- Table 10.1 represents the hydrogen uptake for all of these PIMs at 77 K. Trip- R)-PIMs with shorter all l chains at moderate pressure show excellent H2 adsorption for Trip-(Me)-PIMs, the adsorption of 3.4% by mass at 18 bar is comparable to different types of microporous compounds with similar BET surface areas (Table 10.1). 

Abrahams BF, FitzGerald NJ, Robson R (2010) Cages with tetrahedron-Uke topology formed from the combination of cyclotricatechylene Ugands with metal cations. Angew Chem Int Ed 49 2896-2899... 

Abrahams BF, Boughton BA, FitzGerald NJ, Holmes JL, Robson R (2011) A highly symmetric diamond-hke assembly of cyclotricatechylene-based tetrahedral cages. Chem Commun 47 7404-7406... 

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