Perhydrotriphenylene inclusion compounds

Konig, 0., Burgi, H. B., Armbmster, T., Hulliger, J., Weber, T., A study in crystal engineering Structure, crystal growth, and physical properties of a polar perhydrotriphenylene inclusion compound. J. Am. Chem. Soc. 1997, 119, 10632-10640. 

Quintel, A. Hulliger. 3. Wiibbenhorst, M. Analysis of the polarization distribution in a polar perhydrotriphenylene inclusion compound by scanning pyroelectric microscopy. J. Phys. Chem.. B 1998, 102. 4277-4283. 

J. Gierschner, L. Ltier, D. Oelkrug, E. Musluoglu, B. Behnisch, M. Hanack, Preparation and optical properties of oligophenylenevinylene/perhydrotriphenylene inclusion compounds, Adv. Mater., 12, 757—761 (2002). 

Perhydrotriphenylene (PHTP) is a chiral molecule. The equatorial isomer of PHTP gives rise to a wide variety of inclusion compounds with different kinds of molecules, ranging from those with a nearly spherical or planar... 

The DE approach was shown [102] to be successful in establishing a good approximation of the disordered crystal structure of the perhydrotriphenylene/1-(4-nitrophenyl)piperazine inclusion compound [102], despite the considerable computational effort required for the simulation of diffuse scattering data. This application is also notable for the use of parallel computing concepts to exploit the implicit parallelism of evolutionary algorithms in order to increase computational efficiency. 

The inclusion compounds formed by triangularly shaped hydrocarbon host molecule perhydrotriphenylene... 

Farina. M. Inclusion Compounds of Perhydrotriphenylene. In Inclusion Compounds, Atwood, J.L., Davies, J.E.D.. 

Hulliger, J. Konig, 0. Hoss. R. Polar inclusion compounds of perhydrotriphenylene (PHTP) and efficient nonlinear optical molecules. Adv. Mater. 1995, 7, 719 721. 

Hoss. R. Konig, O. Kramer-Hoss. V. Berger. U. Rogin. P. Hulliger. J. Crystallization of supramolecular materials Perhydrotriphenylene (PHTP) inclusion compounds with nonlinear optical properties. Angew. Chem. Int. Ed. Engl. 1996. 35. 1664-1666. 

Perhydrotriphenylene 70 is of interest because it forms inclusion compounds It is chiral and has been obtained in nonracemic form by peroxide decarboxylation of the acid (71), which could be resolved to apparent enantiomeric purity. A sample of the (-1-) acid (40% optical purity) was degraded to the ketone (72) (+ 332°) This showed a positive Cotton effect in the ORD, at 308-272 nm, allowing assignment of configuration by use of the Octant Rule (72b). A simple four-atom analysis indicates that 70 should have a rotation of — 3k(C—H) or —180°. In contrast with the value for trans-1,2-... 

Figure 1 Molecular structures of some organic molecules that form the host structures in solid inclusion compounds (these specific host structures are encountered freqnently in this chapter) urea, thiourea, tri-orfto-thymotide (TOT), perhydrotriphenylene (PHTP), deoxycholic acid (DCA) and varions molecules related to deoxycholic acid, host A (l,l,6,6-tetraphenylhexa-2,4-diyne-l,6-diol), host B (frans-2,3-bis(hydroxydiphenylmethyl)-l,4-dioxaspiro[5.4]decane), and host C (irans-2,3-bis(hydroxydiphenylmethyl)-l,4-dioxaspiro[5.4]nonane).

Perhydrotriphenylene, C18H30, has the schematic structure shown in Fig. 27 and forms inclusion compounds with... 

In addition to simple binding there are many examples where a low molecular weight species enters either the crystal interior or the interlamellar space with compound formation. These situations, although not uncommon, must obviously be very specific in nature and are termed inclusion compounds or clathrates. An example is given by the phase diagram of Fig. 3.25 for polyethylene-perhydrotriphenylene mixtures.(112) A compound is formed that melts congruently at 178.2 °C. This inclusion compound does not exist in the liquid phase and does not form mixed crystals with the pure species. 

Pure tra i-l,4-polyisoprenes as well as 1,4-polybutadienes can be synthesized by polymerization in inclusion compounds [266-269]. As typical hosts for this dienes, the inclusion compounds or clathrates of urea, thiourea, or perhydrotriphenylene [PHTP Eq. (36)] are used [270,271]. The host forms the frame of the crystal and the guest is placed in the cavities existing in the lattice. Polymerization is generally started by subjecting the inclusion compound to irradiation with a-, y-, or x-rays and proceeds by a radical mechanism [272,273]. Also, free radical initiators such as di-/cr/-butylperoxide could be used [274]. Inclusion in urea yields crystalline trans-, A polymers, whereas trans-lA-polyisoprene obtained in PHTP is amorphous. There is no trace of, A-cis units or of 1,2, 3,4, and cyclic units. The reason for the amorphous product is the presence of a substantial number of head-to-head and tail-to-tail junctions in addition to head-to-jail junctions [275, 276]. 

After that 1,3 pentadiene (XXXIII) was trapped into / -(-)-perhydrotriphenylene (M 93°) (XXXIV) and made it form an inclusion compound, polymerization was carried out under 7-ray irradiation. As a result, trans 1,4-isotactic polypentadiene (XXXV) showing [a] D = 2.5° 0.3° (in chloroform) was yielded. 

Farina et al. [64] found that perhydrotriphenylene (PHTP) serves as a host for inclusion polymerization of various monomers. The PHTP formed inclusion compounds with various monomers and the diffraction studies of the complexes showed that the complexes assume channel-type structures. PHTPs show some structural flexibilities for accommodating guest molecules. They can accommodate not only linear molecules, but also branched and cyclic molecules. Inclusion compounds of PHTP show thermal stability melting points of inclusion compounds are higher than that of each component. 

Among other hosts108 for inclusion and/or clathrate compounds are deoxycholic acid,101 cholic acid,102 small ring compounds such as 29,103 perhydrotriphenylene,104 and the compound 30, which has been called a carcerand.105... 

All-trans-perhydrotriphenylene (PHTP) (cf. insert in Figure 14) is the product of exhaustive hydrogenation of triphenylene. It belongs to one of ten stereoisomers of PHTP. The chiral compound of high rotational symmetry (D3 — C3 -h 3 C2) forms inclusion complexes. The stereoselective polymerization via 7-radiation of the prochiral diolelin 1,3-pentadiene within the chiral nano channels of (.R)-(-)-all-trans-PHTP led to an optically active 1,4-trans-isotactic polymer (Nattaand Farina, 1976) (cf. Figure 13). 

As a natural development of the successful molecular inclusion concept, which involved electrostatic as well as van der Waals forces between the interacting host and guest entities, an increasing interest has been shown in the systematic study of lattice-inclusion type systems. A considerable effort has been devoted to the design of new hosts for the formation of stable crystaUine clathrates and the improvement of selective complexations with potential guests. Suitable examples of clathrates studied in recent years include hosts such as Dianin s compounds , perhydrotriphenylene , cyclotriveratrylene triphenylmethane hexakis-(arylthio) and -(arylthiomethyl)benzenes tri-o-thymotide (TOT) and choleic acids (cf. Fig. 1 in Ch. 1 of Vol. 140). Selected series of such clathrate inclusion systems have particularly been useful in research of photochemical reactions in the solid state and of selective molecular complexation that is central to biological phenomena... 

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