Two aspects of the solid state chemistry of calixarenes are presented : in the first part the chlorination of isopropyl and tert-butylcalixarenes is studied, a mechanism is proposed. In the second part the thermal rearrangement of supramolecular systems p-isopropylcalix[4]arene-p-xylene is discussed, the thermal decapsulation of the guest molecules is schematized.

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The first crystal structure of a calixarene-dye, that of p-tetrakis-(phenylazo)calix[4]arene, is presented in this work. Recrystallization of this purified substance in N,N-dimethylformamide afforded crystals suitable for X-ray diffraction. The compound crystallizes in the triclinic space groupe P1 with a = 14.477(3), b = 15.699(3), c = 11.251(5) Å, x = 95.29(3), β = 89.94(3), γ = 112.35(2)°, and Dc = 1.290g/cm3 for Z = 2. Refinement based on 6932 observed reflections afforded a final R value of 0.089. These calixarene-N,N-dimethyl-formamide 1:1 crystals have a high density for a compound constituted only of hydrogen, oxygen and nitrogen atoms. This is due to the penetration of a benzylazo group of a calixarene molecule in the cavity of a neighbouring calixarene molecule. A hydrogen bond is established between the oxygen atom of the N,N-dimethylformamide and an oxygen atom of the calixarene; CH3…π interactions also exist between an aromatic nucleus of the phenylazo group and N,N-dimethylformamide. The crystal can be described as a series of layers of calixarene molecules and N,N-dimethylformamide molecules in parallel planes. In theory, the two phenyl groups linked by the azo group in the same moiety, which correspond to a conjugated molecule, should be coplanar. This is in fact the case for two moieties. However, interactions within the calixarene cavity disturb the plane of the third phenyl/azophenyl group and create an angle of 25.6° between the two phenyl groups. For the fourth fragment, interactions between the phenylazo group and N,N-dimethylformamide modify the angle between the phenyl group even more significantly (56.5°).

The interaction of iron(III) with the water-soluble calix[6]arene p-sulfonic acid has been studied using potentiometric titrations and near ultraviolet and visible spectrophotometry (T=25 degrees C; mu=0.1 mol L(-1) NaClO4). A characteristic violet-colored complex is formed. Simultaneous exploitation of the neutralization curves, the results of the continuous variations method, and the complementary stimulus coordinates, allows the determination of the stoichiometry of the complex and also the pH range, which varies between pH 2.5 and pH 5.5. A reaction sequence is also suggested.

This paper concerns inclusion complexes of thep-isopropylcalix[4]arene host withp-xylene as guest. It is shown that from a saturated solution inp-xylene, the macrocycle gives a 1 : 1 complex; on heating, the 1 : 1 complex is transformed into a 2: 1 complex, and then into the empty macrocycle. The compounds are studied by differential scanning calorimetry, thermogravimetry and X-ray powder diffraction; the three crystal structures are reported showing the arrangements of the macrocycles with and without their guests.

Water soluble calix [4], calix[6] and calix[8]arene p-sulfonic acids have been synthesized in the solid state in their protonated and hydrated forms. The characterization of the three products was carried out by elementary and thermogravimetric analysis, mass spectrometry, infrared and NMR spectrum determinations. The acid-base behaviour of these potential ligands H8A, H12B and H16C has been determined in aqueous solutions (T = 25-degrees-C; mu = 0.1 mol.L-1 (NaClO4)) by pHmetric titrations and compared with the case of the corresponding monomer which is the p-hydroxybenzene sulfonic acid H2D. All the protonation constants have been estimated or quantitatively determined for the first time. It appears that for the calix[n]arene p-sulfonic acids we have synthesized, it we go from n = 4 to n = 6 and n = 8, certain sulfonic groups become less acidic. The same phenomenon is observed for the hydroxyl groups, as we go from a "superacid" if n = 4 (pK1H < 1) to two groups having pK values of approximately 3.5 and 5.0 if n = 6 and finally to two groups having pK values of 7.5 and 9.0 if n = 8.

It is shown that paraisopropylcalix [4] arene selectively complexes paraxylene from a 1:1:1 mixture of the three xylene isomers. The crystal structures of the complexes of paraisopropylcalix [4] arene with ortho and meta xylenes are isomorphous, crystallizing in the monoclinic group Cc. The complex with paraxylene is tetragonal (group P4/n). In the solid state, the macrocycle loses its 4 symmetry when complexed with ortho or meta xylene. Calculation of intra and intermolecular energies shows that the supramolecular energies are very similar, as are the macrocycle conformation energies of all three complexes. The result is that the phenomenon of molecular recognition observed can either be attributed to the greater number of efficient approaches between paraxylene and the macrocycle, due to its symmetry, in comparison to the other two isomers, or to the higher crystallization rate of the paraxylene complex in the considered medium. These conclusions are in agreement with the fact that crystallization with o- and m-xylene takes place after a much longer time than with p-xylene.

The principle of “the accessibility to reactive centers” is evoked. Its application to 4 solid organic systems brought into reaction with chlorine gas allows the interpretation of the experimental results obtained, thanks to definite knowledge of the crystal structures of these systems. In the cases studied, it can be noted that the reactivity of a phenol molecule in a supramolecular entity decreases when the crystal arrangement consists of supramolecules linked only by Van der Waals type bonds. The reactivity increases for one particular multimolecular system which consists of a three-dimensional hydrogen bond lattice.

ChemInformVolume 21, Issue 13 Reviews ChemInform Abstract: Recent Developments in Calixarenes and Their Properties D. GAMET, D. GAMET Edited by Maruani, J.; Kluwer, Dordrecht, Neth.Search for more papers by this authorM. BOURAKHOUADAR, M. BOURAKHOUADAR Edited by Maruani, J.; Kluwer, Dordrecht, Neth.Search for more papers by this authorL. MEUBLAT, L. MEUBLAT Edited by Maruani, J.; Kluwer, Dordrecht, Neth.Search for more papers by this authorF. LEVEILLER, F. LEVEILLER Edited by Maruani, J.; Kluwer, Dordrecht, Neth.Search for more papers by this authorD. JACQUEMAIN, D. JACQUEMAIN Edited by Maruani, J.; Kluwer, Dordrecht, Neth.Search for more papers by this authorJ. VICENS, J. VICENS Edited by Maruani, J.; Kluwer, Dordrecht, Neth.Search for more papers by this authorR. PERRIN, R. PERRIN Edited by Maruani, J.; Kluwer, Dordrecht, Neth.Search for more papers by this authorV. BOEHMER, V. BOEHMER Edited by Maruani, J.; Kluwer, Dordrecht, Neth.Search for more papers by this author D. GAMET, D. GAMET Edited by Maruani, J.; Kluwer, Dordrecht, Neth.Search for more papers by this authorM. BOURAKHOUADAR, M. BOURAKHOUADAR Edited by Maruani, J.; Kluwer, Dordrecht, Neth.Search for more papers by this authorL. MEUBLAT, L. MEUBLAT Edited by Maruani, J.; Kluwer, Dordrecht, Neth.Search for more papers by this authorF. LEVEILLER, F. LEVEILLER Edited by Maruani, J.; Kluwer, Dordrecht, Neth.Search for more papers by this authorD. JACQUEMAIN, D. JACQUEMAIN Edited by Maruani, J.; Kluwer, Dordrecht, Neth.Search for more papers by this authorJ. VICENS, J. VICENS Edited by Maruani, J.; Kluwer, Dordrecht, Neth.Search for more papers by this authorR. PERRIN, R. PERRIN Edited by Maruani, J.; Kluwer, Dordrecht, Neth.Search for more papers by this authorV. BOEHMER, V. BOEHMER Edited by Maruani, J.; Kluwer, Dordrecht, Neth.Search for more papers by this author First published: March 27, 1990 https://doi.org/10.1002/chin.199013346Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume21, Issue13March 27, 1990 RelatedInformation

AbstractThe reaction of the phenols (I) with the aldehyde (II) leads to the title compounds (III) and calix(8)arenes.

ChemInformVolume 20, Issue 2 Reviews ChemInform Abstract: Solid State Chemistry of Phenols and Possible Industrial Applications R. PERRIN, R. PERRIN Lab. Chim. Ind., Univ. Claude Bernard, 69622 Villeurbanne, Fr.Search for more papers by this authorR. LAMARTINE, R. LAMARTINE Lab. Chim. Ind., Univ. Claude Bernard, 69622 Villeurbanne, Fr.Search for more papers by this authorM. PERRIN, M. PERRIN Lab. Chim. Ind., Univ. Claude Bernard, 69622 Villeurbanne, Fr.Search for more papers by this authorA. THOZET, A. THOZET Lab. Chim. Ind., Univ. Claude Bernard, 69622 Villeurbanne, Fr.Search for more papers by this author R. PERRIN, R. PERRIN Lab. Chim. Ind., Univ. Claude Bernard, 69622 Villeurbanne, Fr.Search for more papers by this authorR. LAMARTINE, R. LAMARTINE Lab. Chim. Ind., Univ. Claude Bernard, 69622 Villeurbanne, Fr.Search for more papers by this authorM. PERRIN, M. PERRIN Lab. Chim. Ind., Univ. Claude Bernard, 69622 Villeurbanne, Fr.Search for more papers by this authorA. THOZET, A. THOZET Lab. Chim. Ind., Univ. Claude Bernard, 69622 Villeurbanne, Fr.Search for more papers by this author First published: January 10, 1989 https://doi.org/10.1002/chin.198902318Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume20, Issue2January 10, 1989 RelatedInformation

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTTheoretical determination of relative stabilities of various polymorphs of organic substances: application on para-substituted phenolsJ. Royer, C. Decoret, B. Tinland, M. Perrin, and R. PerrinCite this: J. Phys. Chem. 1989, 93, 9, 3393–3396Publication Date (Print):May 1, 1989Publication History Published online1 May 2002Published inissue 1 May 1989https://pubs.acs.org/doi/10.1021/j100346a006https://doi.org/10.1021/j100346a006research-articleACS PublicationsRequest reuse permissionsArticle Views49Altmetric-Citations5LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access options Get e-Alerts

Two important precursors of phenolic resins manufactured from phenol are studied. Crystal structures and 13C NMR spectra in solid state are determined for these pure compounds. The thermal polycondensation of one precursor is monitored by 13C NMR.

In order to compare the reactivity of organic molecules in different surroundings in the solid state as well as the selectivity of the reactions to which they give rise under similar conditions, two supramolecular systems have been synthetized. They are: (A) 1:1:1 3,5-dichlorophenol-18-crown-6-water. (B) 2:1:2 3-methyl-2-isopropylphenol-18-crown-6-water The crystalline structures of both (A) and (B) have been determined. They show evidence of the existence of supermolecules in which a water molecule sets up the bridging between the crown ether molecule and the phenol molecule by H-bonding. The results of reactions of the pure solid phenols with gaseous chlorine are compared to those obtained in supramolecular systems (A) and (B) which contain the phenol molecules. The observed differences are well explained on the basis of the crystalline structures and the morphology of crystals.

The isopropyl derivative crystallizes from a mixture of carbon disulfide and benzene in the orthorhombic system: Space groupP21nb, a=17.420(3),b=17.708(3),c=18.972(3) Å,V=5852(3) Å,Z=4. Thet-butyl derivative crystallizes from benzene, but the crystal is a complex (1∶3), space groupPĪ,a=15,065(5),b=19.103(3),c=13.878(3) Å, α=106.95(2), β=102.72(2), γ=80.61(2),V=3703(2) Å3,Z=2. Refinement led toR=0.185 for 1512 reflections for the isopropyl derivative, a sufficiently high number to establish the conformation of the molecule; for thet-butyl complexR=0.12 for 7340 reflections. Intramolecular hydrogen bonds are given as well as comparison of the conformation of both compounds. Thet-butyl groups and the benzene molecules are disordered but the isopropyl groups are not.