Diol Host Compounds Research Articles

Preferential enclathration of lutidine isomers by diol-hosts

The Host compound 2,2ʹ bis(1-hydroxy-4,5-dihydro-2,3:6,7-dibenzocycloheptatrien-1-yl)-biphenyl, H1, has been employed to discriminate between all the pairs of lutidine isomers. The preference for guest enclathration follows the sequence 3,4-LUT>2,4-LUT≈3,5-LUT>2,5-LUT>2,3-LUT>2,6-LUT. This has been confirmed by guest-release endotherms measured by DSC. Four other diol host compounds, H2–H5, were tested on pairs of lutidine isomers which were poorly separated by H1.

Separation of lutidines by enclathration

The selectivity of lutidine isomers by diol host compounds follows the trend: 2,3-LUT ≈ 3,4-LUT > 2,5-LUT > 2,4-LUT > 2,6-LUT.

Host Polymorphs and Crystalline Host–Guest Complexes of 3,3′-Bis(9-hydroxy-9-fluorenyl)biphenyl

The diol host compound 2 featuring a structure with two 9-fluorenol moieties attached in 3,3′-position to a biphenyl core unit has been synthesized and is shown to form crystalline inclusion complexes with organic guest molecules. Aside from the single-crystal X-ray structures of unsolvated 2 in two polymorphous forms (2A, 2B), structures of five inclusion compounds with 1,4-dioxane (2a), DMSO (2b), diethylamine (2c), acetic acid (2d), and ethyl acetate (2e) are described and comparatively discussed in the interaction behavior including corresponding host compounds with different attachment mode of the biphenyl unit and the diphenylhydroxymethyl-substituted equivalent.

Crystalline inclusion compounds of a new diol host featuring a combination of anthracene and 9-fluorenol units

The diol host compound 2 has been synthesised and its behaviour to form crystalline inclusion compounds is discussed in comparison with an analogous ethynylene spaced host compound 1. The rotation around the fluorenol–anthracene bonds in 2 is highly restricted as indicated by solution NMR spectroscopy, molecular mechanics and semi-empirical calculations. Single-crystal X-ray structures of the inclusion complexes of 2 with 1-BuOH (2a), morpholine/H2O (2b) and DMSO (2c) are in agreement with the bent geometry of the anthracene ring system suggested by the calculations. The structures exhibit specific modes of hydrogen bond interactions.

The Dutch Resolution Method: Attempted Enhanced Selectivity of 2-Butylamine with Mixed Diol Hosts

The Dutch resolution method was employed to resolve 2-butylamine. Four similar diol host compounds were utilized singly and in combination to obtain inclusion compounds that displayed partial enantiomeric selectivity. However, the combination of any pair of host compounds did not significantly improve the enantiomeric excess of the 2-butylamine over that given by single host compounds. We attribute the results to the constant packing patterns of the structures.

Enhanced enantioselectivity of 3-methylcyclohexanone by mixed diol host compounds

3-Methylcyclohexanone is only partially resolved by crystallisation with a chiral diol host compound (ee 40%), but when recrystallised from an equimolar mixture of the chiral diol host and a similar but achiral host we obtain complete resolution. The latter host acts as a nucleation inhibitor and the enhanced resolution is attributed to kinetic effects.

Polymorphism, isomorphism and variability in the inclusion chemistry of a diol host compound

Polymorphism, isomorphism and variability in the inclusion chemistry of a diol host compound

Polymorphism, isostructurality and variability in the inclusion chemistry of a diol host compound

The diol host compound 2,2′-bis(hydroxydiphenylmethyl)-1,1′-binaphthyl crystallised in three different polymorphic structures, and formed a series of inclusion compounds with pyridine, morpholine and benzene. Different stoichiometries were obtained by manipulating the proportions of the guests and the crystallisation temperatures. A number of these compounds are isostructural and the guests are located at fixed sites in the crystal structure. Structural similarities were interpreted via Hirshfeld surface fingerprint plots. The results of thermal analysis of one structural group were explained in terms of the host⋯guest interactions.

A bis(hydroxydiphenylmethyl) substituted 1,1′-binaphthyl diol host compound: polymorphism and clathrates with multiple guest species

A bis(hydroxydiphenylmethyl) substituted 1,1′-binaphthyl diol host compound: polymorphism and clathrates with multiple guest species

Inclusion properties of quinolines by a diol host compound

1,4-bis(9-hydroxyfluoren-9-yl)benzene (H) is a versatile host compound which conforms to EdwinWeber’s host design specifications in that the molecule is rigid and bulky and contains hydroxyl moieties, which are good hydrogen-bond donors. In literature, this compound has been employed for the separation of the isomers of lutidine [1] and for the guest exchange between acetone and DMSO . The guest selectivity between aniline and benzylamine by this host has been studied and was found changed dramatically by controlling PH . In this study we investigate the inclusion properties of the host compound towards quinoline(Q), 2-methylquinoline (2MeQ), 6-methylquinoline (6MeQ) and 8-methylquinoline (8MeQ) ( see Scheme). All the guests formed inclusion compounds with the same host:guest ratio. Single x-ray crystal structures of the inclusion compounds have been elucidated and are all stabilised by (host)O-HcccN(guest) hydrogen bonds. Thermal stabilities were studied by Thermogravimetry (TG). Competition experiments were carried out to study the guest selectivity.

Complexation with diol host compounds. Part 36: inclusion compounds of 1,1,6,6-tetraphenylhexa-2,4-diyne-1,6-diol with benzene, toluene and mesitylene

The title compound 1,1,6,6-tetraphenylhexa-2,4-diyne-1,6-diol (H) forms inclusion compounds with benzene, toluene and mesitylene. H·C6H6 (1) and H· $$\frac{3}{4}$$ C7H8 (2) crystallize in the triclinic space group P(-1) with unit cell dimensions for 1: a = 13.001(3) A, b = 15.284(3) A, c = 16.744(3) A, α = 99.26(3)°, β = 74.78(3)°, γ = 64.96(3)°, Z = 4 and for 2: a = 12.922(3) A, b = 15.159(3) A, c = 16.562(3) A, α = 68.12(3)°, β = 73.99(3)°, γ = 66.00(3)°, Z = 4. The hydroxyl groups of adjacent host molecules are involved in hydrogen bonding. H·C9H12 (3) exhibits a different packing arrangement with weak hydrogen bonding between the hydroxyl hydrogen of the host and the phenyl ring of the guest. The crystal system of compound 3 is monoclinic with space group C2/c, a = 23.750(5) A, b = 8.4746(17) A, c = 17.760(4) A, α = 90°, β = 123.40(3)°, γ = 90°, Z = 4. The thermal behaviour of these compounds has also been studied.

Complexation with Diol Host Compounds. Part 35: Inclusion Compounds of 1,1,6,6-Tetraphenylhexa-2,4-diyne-1,6-diol with CCl4, CHCl3, CH2Cl2 and CH3CN

Inclusion compounds were formed with 1,1,6,6-tetraphenylhexa-2,4-diyne-1,6-diol (H) and carbon tetrachloride, chloroform, dichloromethane and acetonitrile. 1 (H·1/2CCl4), 2 (H·1/2CHCl3) and 3 (H·1/2CH2Cl2) are true clathrates with the guest molecules situated in cages created by the host. 4 (H·2CH3CN) exhibits a different packing arrangement with the guest molecules located in channels. The crystal structures and stability of these inclusion compounds were investigated.

Inclusion compounds of 1,1,6,6-tetraphenylhexa-2,4-diyne-1,6-diol with DMF and DMSO: structures, selectivity and kinetics of desolvationComplexation with diol host compounds. Part 34. For Part 33, see ref. 3.

Download options Please wait... Supplementary files Crystal structure data TXT (30K) Article information DOI https://doi.org/10.1039/B302548A Article type Paper Submitted 05 Mar 2003 Accepted 01 May 2003 First published 15 May 2003 Download Citation CrystEngComm, 2003,5, 150-153 BibTex EndNote MEDLINE ProCite ReferenceManager RefWorks RIS Permissions Request permissions Inclusion compounds of 1,1,6,6-tetraphenylhexa-2,4-diyne-1,6-diol with DMF and DMSO: structures, selectivity and kinetics of desolvation M. R. Caira, A. Jacobs, L. R. Nassimbeni and F. Toda, CrystEngComm, 2003, 5, 150 DOI: 10.1039/B302548A To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page. If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given. If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page. Read more about how to correctly acknowledge RSC content. Social activity Tweet Share Search articles by author Mino R. Caira Ayesha Jacobs Luigi R. Nassimbeni Fumio Toda

Inclusion by a diol host compound: structure and dynamics of volatile guest exchange

1,1,6,6-Tetraphenylhexa-2,4-diyne-1,6-diol (H) forms inclusion compounds with furan (1 and 2), tetrahydrofuran (3) and thiophene (4). 1, H·½FUR (H ∶ G = 1 ∶ ½), is a true clathrate, with the furan guest located in a cage formed by the host. The remaining structures (H ∶ G = 1 ∶ 2) 2, H·2FUR, 3, H·2THF and 4, H·2THIO are isostructural with guests located in channels. Selectivity and guest exchange reactions have been analysed and correlated to the topologies of the inclusion compounds.

Complexation with diol host compounds. Part 33. Inclusion and separation of pyridines by a diol host compound

The host 1,1,6,6-tetraphenylhexa-2,4-diyne-1,6-diol includes pyridine and the picolines. The structures of these inclusion compounds and their lattice energies have been determined. The selectivity of the host for a particular guest has been measured by competition experiments and the results are rationalised in terms of the structural features of the host-guest compounds.

Inclusion of Aminobenzonitrile Isomers by a Diol Host Compound: Structure and Selectivity

1,1,6,6-Tetraphenylhexa-2,4-diyne-1,6-diol (H) forms inclusion compounds with 2-, 3-, and 4-aminobenzonitrile (2ABN, 3ABN, and 4ABN). In each case the host:guest ratio is 1:2 and the structures are stabilized by hydrogen bonds. Competition experiments show that the host selects the guests in order of preference of 2ABN > 3ABN > 4ABN. These results are in general agreement with lattice energy calculations, thermal analyses, and solid-state reactions. The structure of the solid formed between H and a mixture of 3ABN and 4ABN has also been elucidated.

Complexation with diol host compounds. Part 32.† Separation of lutidine isomers by 1,1,6,6-tetraphenylhexa-2,4-diyne-1,6-diol

The title host compound forms inclusion compounds with 2,4-, 3,5- and 2,6-lutidine. In each case the host∶guest ratio is 1∶2 and the structures are stabilised by (Host)O–H· · ·N(Guest) hydrogen bonds. Competition experiments show that the host selects the guests in order of preference of 3,5-lutidine > 2,6-lutidine > 2,4-lutidine. These results are in general agreement with the lattice energy calculations.

Inclusion and Separation of Lutidine Isomers by a Diol Host Compound

Structures of the inclusion compounds formed between the host compound 1, 1-bis(4-hydroxyphenyl)cyclohexane and selected lutidine isomers have been elucidated. The activation energies and kinetics of desolvation for the complexes were determined. Competition experiments were performed to investigate preferential enclathration. Lattice energy calculations explain the results of the competition experiments.

Selective inclusion of aliphatic alcohols by a diol host compound

An aliphatic alcohol mixture is separated using enclathration methods, and the results are explained by means of lattice energy calculations and structural analysis.

Inclusion and separation of picoline isomers by a diol host compound

Structures of the inclusion compounds formed between the host compound 1,1-bis(4-hydroxyphenyl)cyclohexane and the isomers of picoline have been elucidated. The activation energies and the kinetics of desolvation for the complexes have been determined. Competition experiments have been performed to investigate which isomer is preferentially enclathrated by the host. Lattice energy calculations explain the results of the competition experiments.