Diol Host Compounds Research Articles

Complexation with diol host compounds. Part 25.1 Selective inclusion of benzenediol isomers by 1,1-bis(4-hydroxyphenyl)cyclohexane

The title host compound includes all the isomers of the benzenediols. The structures with the p- and o-benzenediols have been elucidated and show that the clathrates are stabilised by hydrogen bonds. Competition experiments with the host in water suspension show that the para-isomer is preferentially enclathrated. Lattice energy calculations explain the results of the competition experiment.

Structural chemistry and guest inclusion of a new supramolecular material showing sensitivity to organic solvent vapors

Clathrate formation—the formation of crystalline inclusion compounds—is one approach to chemical sensing of vapors and gases. The synthesis of a new diol host compound is described and absorptive clathrate formation and thermal clathrate decomposition are reported for acetone as the guest. It is shown that the sorptive uptake of a guest vapor by the crystalline host compound is not merely surface adsorption but true clathrate formation, involving a solid‐state transformation. It is suggested that the use of the host as a chemical sensor is not far off.

Complexation with diol host compounds. Part 24. Kinetics of desolvation of inclusion compounds of 2,7-substituted 2,2′-bis(9-hydroxy-9-fluorenyl)biphenyl hosts with acetone

The structures of the acetone inclusion compounds of 2,2′-bis(2,7-dichloro-9-hydroxy-9-fluorenyl)biphenyl (compound 1) and 2,2′-bis(2,7-di-tert-butyl-9-hydroxy-9-fluorenyl)biphenyl (compound 2), with host∶guest ratios of 1∶2 and 1∶1, respectively, have been elucidated. Compound 2 desolvates at 175 °C, whereas compound 1 is much less stable and desolvates at 80 °C. Compound 1 desolvates in a single deceleratory step following a three dimensional diffusion kinetic model. The desolvation of compound 2 follows the first-order kinetic model. The activation energies of desolvation have been evaluated.

Complexation with diol host compounds. Part 18. Structures and thermal analysis of trans-9,10-dihydroxy-9,10-di-p-tolyl-9,10-dihydroanthracene and its inclusion compounds with acetone, diethyl ether and pyridine

Abstract The structure of the host compound trans-9,10-dihydroxy-9,10-di-p-tolyl-9,10-dihydroanthracene and those of its inclusion compounds with acetone, diethyl ether and pyridine have been elucidated. The non-porous α-phase of the host has a structure in which the molecules are packed in layers parallel to the (100) plane, but exhibit no intermolecular hydrogen bonding. The host:guest stoichiometry of each inclusion compound is 1:2, and the structures are each stabilised by O-H…O or O-H…N hydrogen bonds between host and guest. The thermal decompositions of the acetone and diethyl ether compounds are characterised by single endotherms of the guest-release reaction, but the pyridine inclusion compound has a more complex decomposition, characteristic of similar pyridine inclusion compounds.

Complexation with diol host compounds. Part 17. Structures and thermal analysis of 9,9′-dihydroxy-9,9′-bifluorene with ethanol, 1-butanol and pyridine

Abstract Structures of the inclusion compound 9,9′-dihydroxy-9,9′-bifluorene with ethanol, 1-butanol and pyridine have been determined. The structures are stabilised by networks of hydrogen bonds. The thermal analysis indicates a single step decomposition process with concomitant phase transition of the structures. Accurate vapour pressure measurements at various temperatures yield the enthalpy change for the guest release reaction.

Complexation with diol host compounds. Part 20. Kinetics of desolvation of inclusion compounds of 2,2′-bis(2,7-dichloro-9-hydroxy-9-fluorenyl)biphenyl with 1,4-dioxane and 1,3-dioxolane

The structures of the inclusion compounds of 2,2′-bis(2,7-dichloro-9-hydroxy-9-fluorenyl)biphenyl with 1,4-dioxane and 1,3-dioxolane, with host : guest ratios of 1: 3.5 and 1: 2 respectively, have been elucidated. Their kinetics of desolvation have been studied and the dioxane inclusion compound desolvates in two distinct steps, each following the first-order kinetic model. The dioxolane inclusion compound desolvates in one step and follows a contracting area model. X-Ray powder photography shows that the dioxane inclusion compound forms a stable intermediate γ-phase before final desolvation to a non-porous α-phase.

Complexation with diol host compounds, part 161. Structure and thermal stability of 2,2′-bis(9-hydroxy-9-fluorenyl)biphenyl.diethyl ether

Abstract The structure of the inclusion compound of 2,2′-bis(9-hydroxy-9-fluorenyl)biphenyl (1) with diethyl ether (2) (1:1) is reported. Crystal data: monoclinic, P21/n with a = 11.728(7), b = 20.471(4), c = 14.334(8) Å, β = 109.23(7)°, Z = 4, Dc = 1.20 g cm−3. The final R value was 0.045 for 3479 reflections. The inclusion compound displays a high thermal stability. The enthalpy of the guest release reaction and the activation energy of thermal decomposition have been measured. The crystal structure shows diethyl ether to be tightly packed in cavities formed by the host compound. The structure is further stabilized by host-guest hydrogen bonding.

Complexation with diol host compounds. Part 19. Structures and thermal analyses of inclusion compounds oftrans-9,10-dihydroxy-9,10-diphenyl-9,10-dihydroanthracene with dimethylsulphoxide, diethylketone and (±)-2-butanol

The structures of the host compoundtrans-9,10-dihydroxy-9,10-diphenyl-9,10-dihydroanthracene with dimethylsulphoxide (1∶2), diethyl ketone (1∶1) and (±)-2-butanol (1∶1) have been elucidated. Each compound is stabilized by O−H...O hydrogen bonds between host and guest, and the guest molecules are disordered in each structure. The thermal decomposition of the compounds shows them to be relatively unstable.

Solid-state photosolvolysis of clathrate crystals including ethanol as a guest component

The guest ethanol molecules in the clathrate crystals reacted photochemically with the diol host compounds, bis(9-hydroxyfluoren-9-yl)thieno[3,2-b]- and [2,3-b]-thiophenes, to cause photosubstitutions in the solid-state.

Complexation with diol host compounds. 13. Crystal structures and thermal analyses of inclusion compounds of 1,1,6,6-tetraphenylhexa-2,4-diyne-1,6-diol with cyclohexane,O-xylene,m-xylene andp-xylene

Abstract It has been shown that host compound 1,1,6,6-tetraphenylhexa-2,4-diyne-1,6-diol is able to include polar guests and now we report on its ability to form clathrate compounds with apolar guests. The structures of this host with cyclohexane (1) and the ortho (2), meta (3) and para (4) xylenes have been determined and are discussed. Crystal data: (1) 2C30H22O2C6H12, M r = 913.20 g mol−1, mono-clinic, C2/c, a = 22.851(6), b = 14.010(2), c = 17.076(6) A, β = 108.71(3)°, V = 5178(2) A3, Z = 4, D c = 1.17g cm−3, N = 3326, R = 0.092. (2) 2C30H22O21 ½C8H10, M r = 1976.5 g mol−1, triclinic, P 1, a = 13.185(3), b = 15.466(3), c = 16.573(2) A, α = 96.39(13)°, β = 106.96(15)°, γ = 114.94(18)°, V = 2822(2) A3, Z = 2, D c = 1.16 g cm−3, N = 6152, R = 0.075. (3) 2C30H22O21 ½C8H10, M r = 1976.5 g mol−1, triclinic, P 1, a = 13.267(5), b = 15.453(3), c = 16.654(5) A, α = 97.12(2)°, β = 107.09(3)°, γ = 114.68(3)°, V = 2843(2) A3, Z = 2, D c = 1.15 g cm−3, N = 6505, R = 0.083. (4) 2C30H22O21 ½C8H10, M r = 1976.5 g mol...

Complexation with Diol Host Compounds, 12. Synthesis and Solid‐State Inclusion Properties of Bis(diarylhydroxymethyl)1‐Substituted 1,1′‐Binaphthyls. Crystal Structures of a Host and Its Pyridine Clathrate

A series of new clathrate host molecules 1 – 8 containing two bis(diarylhydroxymethyl) groups attached to different positions (2,2′ or 8,8′) of a 1,1′-binaphthyl frame have been synthesized. Their clathrate formation properties with organic guests including alcohols, amines, ketones, and other dipolar aprotic compounds or aromatic hydrocarbons are reported (74 examples of clathrates) together with the results of solvent competition experiments for the parent host compound. The inclusion formation and the clathrate stoichiometries depend on the structure of the host molecules in a systematic manner. The crystal structures of the free parent host 1 and its pyridine clathrate (1 : 3) have been determined by X-ray diffraction. The molecular structure of the host is similar in the two species involving an intramolecular hydrogen bond between the host hydroxyls. No other hydrogen bond is involved in the free host case while in the pyridine inclusion compound the second host hydroxyl forms a hydrogen bond with the nitrogen of one pyridine guest which is surrounded by two unbound pyridine species such as to form clusters of three pyridine guests enclosed in the cavities between the host molecules. Thermal analysis corresponds with the two binding states of the pyridine molecules in the clathrate.

Complexation with diol host compounds. Part 14. Inclusion compounds of 2,2′-bis(9-hydroxy-9-fluorenyl)biphenyl with acetonitrile, cyclohexanone, di-n-propylamine and dimethylformamide

Abstract The structures of the inclusion compounds of 2,2′-bis(9-hydroxy-9-fluorenyl)biphenyl (H) with acetonitrile (1) (1:1), cyclohexanone (2) (1:2), di-n-propylamine (3) (1:1) and dimethylformamide (4) (1:2) are reported. Crystal data: (1) monoclinic, P21/c with a=10.500(3), b=15.598(3), c=18.344(3) A, β=96.66(2)°, Z=4, D C=1.24 g cm−3. (2) monoclinic, P21/c with a=13.980(3), b=11.768(5), c=23.49(1) A, β=98.77(3)°, Z=4, Dc =1.24 g cm−3. (3) monoclinic, C2/c with a=29.57(1), b=13.485(4), c=18.17(1) A, β=107.94(4)°, Z=8, D C=1.16 g cm−3. (4) monoclinic, C2/c with a=30.123(9), b=13.391(6), c=19.177(6) A, β=111.23(4)°, Z=8, D C=1.22 g cm−3. Final R values for the four structures were 0.065, 0.120, 0.084 and 0.107 for 2937, 2830, 2071 and 3769 reflections, respectively. The host conformation is quite rigid and does not appear to be influenced by the shape and size of the guests studied. The host is held in a spiral conformation by means of an intramolecular hydrogen bond. In addition, host-guest hydrogen bo...

Complexation with diol host compounds. 8. Structures and thermal analysis of 1,1,6,6-tetraphenylhexa-2,4-diyne-1,6-diol with selected ketones

The structures of three inclusion compounds of 1,1,6,6-tetraphenylhexa-2,4-diyne-l ,6-diol with methyl ethyl ketone (1), diethyl ketone (2) and acetophenone (3) have been determined and their thermal decomposi t ion investigated by thermogravimetry and differential scanning calorimetry. Crystal data are: (1), C30H2202.2C4H80, Mr = 558.72, monoclinic, P2~/n, a = 8.321 (3), b = 11.845 (3_), c = 17.153 (4)/k, /3 = 100.35 (2) °, V = 1663 (1) A 3, Z = 2, O m = 1.09 (3), Dx = 1.12 g c m -3, Mo Ka, A = 0.7107/~, /z = 0.39 cm-1, F(000) = 596, T = 294 K, final R = 0.073 (wR = 0.084) for 1494 independent reflections. (2), C3oH220>2CsHloO, M r = 5 8 6 . 7 7 , monoclinic, P2,/n, a = 10.108 (2), b = 8.579 (1), c = 20.536 (2)/k, / 3 = 1 0 2 . 4 5 ( 1 ) °, V = 1 7 3 8 . 9 ( 4 ) A 3, Z = 2 , Dr,,= 1.10 (2), Dx = 1.12 g cm -3, Mo Ka, A = 0.7107/k, /z = 0.33 c m ~, F(000) = 628, T = 294 K, final R = 0.081 (wR = 0.090) for 1818 independent reflections. (3), C30H2202.2CsH80, Mr = 654.80, triclinic, P1, 0108-7681/92/060827-06506.00 a = 11.204 (4), b = 11.856 (6), c = 16.236 (6)/k, a = 6 9 . 5 0 ( 4 ) , / 3 = 7 9 . 3 2 ( 3 ) , y = 6 2 . 9 8 ( 4 ) , V = 1799 (2) A 3, Z = 2, Dm = 1.20 (1), Dx = 1.21 g cm -3, Mo Ka, A = 0.7107 ./k, p, = 0.41 cm-1 , F(000) = 692, T = 2 9 4 K , final R = 0 . 0 9 6 ( w R = 0 . 1 0 2 ) for 2106 independent reflections.

Complexation with diol host compounds: Part 9. Structures and thermal analyses of inclusion compounds of trans-9,10-dihydroxy-9,10-diphenyl-9,10- dihydroanthracene with acetonitrile and 3-hydroxypropionitrile

The host compound ( H), trans-9,10-dihydroxy-9,10-diphenyl-9,10-dihydroanthracene forms inclusion compounds with acetonitrile (compound 1) and 3-hydroxypropionitrile (compound 2) both with host : guest ratio of 1:2. Crystal data: ( 1) C 26H 20O 2·2C 2H 3N, M r = 446.54, a = 8.530(2), b = 16.995(6), c = 9.034(1) Å, β = 109.15(2)°, space group P2 1/c , D m = 1.18 g cm −3, D c = 1.20 g cm −3 for Z = 2, R = 0.096 for 1363 reflections; ( 2) C 26H 20O 2·2C 3H 5NO, M r = 506.60, a = 8.444(1), b = 9.7931(7), c = 16.558(2) Å, β = 104.32(1)°, space group P2 1nD m = 1.28 g cm −3, D c = 1-27 g cm −3 for Z = 2, R = 0.066 for 1567 reflections. The thermal decomposition of (1) shows that the guest release reaction occurs in a single step, but that the activation energy varies with the extent of decomposition, from 83 to 114 kJ mol −1. DSC of ( 2) shows that decomposition is more complex, with possible phase changes of the host structure.

Complexation with diol host compounds. Part 10. Synthesis and solid state inclusion properties of bis(diarylhydroxymethyl)-substituted benzenes and biphenyls; X-ray crystal structures of two host polymorphs and of a non-functional host analogue

A new family of host molecules where the molecular axis of usual ‘wheel-and-axle’ compounds is replaced by aromatic units is described. These diol hosts form crystalline inclusions with a variety of uncharged organic molecules mainly of a polar nature (53 different copecies). The formation and stoichimetry depend in a systematic manner on structural parameters of the host allowing these hosts to be more selective than the parent compounds. Non-hydroxylic analogues do not function as host molecules. The crystal structures of two polymorphs of host compound 2 and of the inefficient compound 9 have been studied. Crystal data: 2(polymorph α1), monoclinic, C2/c, a= 16.827(2), b= 15.212(3), c= 10.708 Å, β= 97.01(1)°, V= 2721 Å3, Z= 4; 2(polymorph α2), triclinic, P, a= 8.807(2), b= 10.687(6), c= 16.263(3)Å, α= 100.97(3)°, β= 91.47(2)°, γ= 113.02(3)°, V= 1375 Å3, Z= 2; 9, monoclinic, P21/n, a= 12.781(3), b= 7.773(2), c= 28.405(17)Å, β= 103.01°, V= 2749 Å3, Z= 4. Alignment of the axis of the molecular backbones was observed in all structures. Formation of host-host hydrogen bonds in the case of the α2-polymorph of 2 resulted in a gauche conformation of the hydroxy moieties unlike the α1-polymorph of 2 which is anti. The packing factors are 17.00, 17.18 and 18.09 Å3 per non-hydrogen atom for 2(α1), 2(α2) and 9, respectively.

Complexation with diol host compounds. Part 11. Structures and thermal analyses of the inclusion compounds of 4,4′-bis(diphenylhydroxymethyl)biphenyl, C38H30O2, with acetone, acetophenone, 1,4-dioxane and p-xylene

Structures of the inclusion compounds of 4,4′-bis(diphenylhydroxymethyl)biphenyl with acetone (1), acetophenone (2), 1,4-dioxane (3) and p-xylene (4) have been determined. Crystal data: 1; C38H30O2·2C3H6O, Mr= 634.81 g mol–1, orthorhombic, Pna21, a= 29.169(6), b= 8.046(1), c= 15.235(2)A, V= 3576(1)A3, Z= 4, Dm= 1.17(3) g cm–3, Dc= 1.18 g cm–3, λ(Mo-Kα)= 0.710 69 A, µ= 0.39 cm–1, F(000)= 1316.2; C38H30O2·2C8H8O, triclinic, P, Mr= 758.95 g mol–1, a= 8.005(6), b= 11.464(3), c= 12.338(3)A, α= 85.14(2), β= 76.89(4), γ= 73.71(4)°, V= 1058(1)A3, Z= 1, Dm= 1.17(2) g cm–3, Dc= 1.19 g cm–3, λ(Mo-Kα)= 0.71069 A, µ= 0.40 cm–1, F(000)= 402. 3; C38H30O2·2C4H8O2, Mr= 654.80 g mol–1, monoclinic, P21/n, a= 9.434(2), b= 14.152(5), c= 14.503(1), β= 105.36(1)°, V= 1866(1)A3, Z= 2, Dm= 1.20(2) g cm–3, Dc= 1.22 g cm–3, λ(Mo-Kα)= 0.71069 A, µ= 0.44 cm–1, F(000)= 836. 4; C38H30O2·1.75C8H10, Mr= 1408.89 g mol–1, monoclinic, P21/n, a= 20.354(3), b= 21.142(4), c= 21.327(4)A, β= 117.92(1)°, V= 8109(3)A3, Z= 8, Dm= 1.15(2) g cm–3, Dc= 1.15 g cm–3, λ(Mo-Kα)= 0.710 69 A, µ= 0.71 cm–1, F(000)= 3004. Depending on the host–guest interaction, they are H-bonded coordinatoclathrates in the case of 1–3 and a true clathrate type of inclusion compound in the case of 4 with H-bonded tetramer clusters of host molecules forming the inclusions matrix. The thermal decompositions of the compounds have been studied. Compound 1 contains acetone molecules in two different binding states, one being more strongly bound than the other giving two individual endotherms. Phase transitions before the melting point occur in compounds 1,3 and 4. Compound 2 shows no melting point because of dissolution of the host compound in the released guest.

Complexation with diol host compounds. Part 6. Structure and dynamics of enclathration by 1,1,6,6-tetraphenyl-hexa-2,4-diyne-1,6-diol

The host compound 1,1,6,6-tetraphenyl-hexa-2,4-diyne-1,6-diol forms inclusion compounds with acetone( Pbca) and benzophenone( P2 1 c ). The structures of the nonporous α-phase of the host ( P1 bar), as well as those of the host-guest compounds, have been elucidated. The kinetics of the reaction of the host with both these guest molecules have been analyzed.

Complexation with diol host compounds. 4. 1:1 molecular complexes of 1,1-bis(4-hydroxyphenyl)cyclohexane with water and ethanol

C 18 H 20 O 2 •H 2 O (I) cristallise dans P2 1 avec a=10,779, b=6,499, c=10,962 A, β=97,54 o , Z=2; affinement jusqu'a R=0,036. C 18 H 20 O 2 •C 2 H 6 O (II) cristallise dans P1 avec a=6,292, b=10,864, c=13,425 A, α=84,76, β=77,95, γ=78,95 o , Z=2; affinement jusqu'a R=0,049. Les associations intermoleculaires entre la molecule hote et la molecule «invitee» dans les deux structures sont caracterisees par un arrangement triangulaire efficace de liaisons hydrogene «accepteur-donneur» avec les longueurs O...O allant de 2,588 a 2,774 A

Complexation with diol host compounds. Part 7. Structures and thermal analysis of 1,1,2,2-tetraphenylethane-1,2-diol with lutidine guests

Structures of the inclusion compounds of 1,1,2,2-tetraphenylethane-1,2-diol with 2,6-lutidine (1), 3,5-lutidine (2) and 3,4-lutidine (3) have been determined. Crystal data: (1) C26H22O2·C7H9N, Mr= 473.62, triclinic, P, a= 9.414(7), b= 11.191(4), c= 13.328(18)A, α= 82.81 (7), β= 70.78(12), γ= 86.44(4)°, V= 1315.2 A3, Z= 2, Dm= 1.17, Dc= 1.20 g cm–3, λ(Mo-Kα)= 0.710 69 A, µ= 0.40 cm–1, F(000)= 504. (2) C26H22O2·(C7H9N)2, Mr= 580.77, triclinic, P, a= 12.099(4), b= 17.869(5), c= 17.873(10)A, α= 64.65(3), β= 87.32(4), γ= 75.25(2)°, V= 3368.4 A3, Z= 4, Dm= 1.12, Dc= 1.15 g cm–3, λ(Mo-Kα)= 0.71069 A, µ= 0.64 cm–1, F(000)= 1240. (3) C26H22O2·(C7H9N)2, Mr= 580.77, triclinic, P, a= 9.163(4), b= 11.740(4), c= 17.721 (7)A, α= 69.50(3), β= 74.22(4), γ= 73.09(4)°, V= 1677.2 A3, Z= 2, Dm= 1.14, Dc= 1.15 g cm–3, λ(Mo-Kα)= 0.710 69 A, µ= 0.38 cm–1, F(000)= 620. The final R values at 293 K were (1) 0.043, (2) 0.070 and (3) 0.067 for 3382, 8561 and 4828 unique reflections. Strong host–guest hydrogen bonding is observed in all structures, O ⋯ N distances are between 2.664 and 2.889 A. Thermal analysis revealed the strength of binding of the guest molecules and a competition experiment showed that 3,5-lutidine is preferentially included over 2,6-lutidine.

Complexation with diol host compounds. 5. Structures and thermal analyses of inclusion compounds of trans-9,10-dihydroxy-9,10-diphenyl-9,10-dihydroanthracene with 2-butanone, 4-vinylpyridine, 4-methylpyridine and 2-methylpyridine

C 26 H 20 O 2 .C 4 H 8 O cristallise dans P1 avec a=7,924, b=8,827, c=9,050A α=109,93, β=97,31, γ=97,65°, Z=1; affinement jusqu'a R=0,059. C 26 H 20 O 2 .2C 7 H 7 N cristallise dans P21/c avec a=10,045, b=18,630, c=8,419A, β=96,29°, Z=2 ; affinement jusqu'a R=0,054. C 26 H 20 O 2 .2C 6 H 7 N cristallise dans P1 avec a=8,371, b=9,599, c=10,182A, α=71,12, β=82,05, γ=74,45°, Z=1; affinement jusqu'a R=0,040. C 26 H 20 O 2 .C 6 H 7 N cristallise dans P1 avec a=9,337, b=10,407, c=13,470A, α=70,75, β=87,65, γ=73,58°, Z=2; affinement jusqu'a R=0,060