Arene-perfluoroarene interactions in crystal engineering: Structural preferences in polyfluorinated tolans

Caroline E. Smith, Philip S. Smith, Rhodri Ll Thomas, Edward G. Robins, Jonathan C. Collings, Chaoyang Dai, Andrew J. Scott, Simon Borwick, Andrei S. Batsanov, Stephen W. Watt, Stewart J. Clark, Christopher Viney, J. A K Howard, Clegg William, Todd B. Marder

Research output: Contribution to journalArticle

Abstract

The compounds 4-ROC6F4C=Ph (4) where R = Me (a), Et (b), Prn (c), Pri (d), Bun (e), W-C5H11 (f), PhCH2 (g), PhCH2CH 2 (h), 4-MeC6H4 (i), 4-EtC6H 4 (j) and menthyl (k), have been prepared by reaction of C 6F5C=CPh (3) with ROH in the presence of KOH, and characterised by NMR (1H, 13C, 19F) and mass spectroscopy. The single-crystal structures of PhC=CPh·C 6F5C=CC6F5 (1:2), 3 and 4a,c,d,f,g,i have been determined by X-ray diffraction at 120-160 K, and that of 3 also calculated by an ab initio pseudo-potential DFT method. The tolan moiety is nearly planar in each molecule except 4a, which has a Ph/C 6F5 dihedral angle of 25.8°. The R group adopts an out-of-plane orientation except in 4f, where the n-pentyl chain is nearly coplanar with the C6F5 group at the cost of severe distortion of the C(ar)-C(ar)-O angles (which differ by 13.5°). The structures of 1:2, 3 (pseudo-isomorphous with 1:2), 4a, 4g (disordered) and 4i contain stacks of alternating arene and perfluoroarene moieties; 4c and 4d form discrete centrosymmetric dimers with arene/ perfluoroarene overlap, while 4f forms infinite stacks without such overlap. Differential thermal analysis and transmitted polarised light microscopy revealed no liquid-crystalline behaviour of 3 and 4.

Original languageEnglish
Pages (from-to)413-420
Number of pages8
JournalJournal of Materials Chemistry
Volume14
Issue number3
Publication statusPublished - 7 Feb 2004

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Crystal engineering
Dihedral angle
Light polarization
Discrete Fourier transforms
Dimers
Differential thermal analysis
Optical microscopy
Crystal structure
Nuclear magnetic resonance
Single crystals
Spectroscopy
Crystalline materials
X ray diffraction
Molecules
Liquids

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Smith, C. E., Smith, P. S., Thomas, R. L., Robins, E. G., Collings, J. C., Dai, C., ... Marder, T. B. (2004). Arene-perfluoroarene interactions in crystal engineering: Structural preferences in polyfluorinated tolans. Journal of Materials Chemistry, 14(3), 413-420.
Smith, Caroline E. ; Smith, Philip S. ; Thomas, Rhodri Ll ; Robins, Edward G. ; Collings, Jonathan C. ; Dai, Chaoyang ; Scott, Andrew J. ; Borwick, Simon ; Batsanov, Andrei S. ; Watt, Stephen W. ; Clark, Stewart J. ; Viney, Christopher ; Howard, J. A K ; William, Clegg ; Marder, Todd B. / Arene-perfluoroarene interactions in crystal engineering : Structural preferences in polyfluorinated tolans. In: Journal of Materials Chemistry. 2004 ; Vol. 14, No. 3. pp. 413-420.
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title = "Arene-perfluoroarene interactions in crystal engineering: Structural preferences in polyfluorinated tolans",
abstract = "The compounds 4-ROC6F4C=Ph (4) where R = Me (a), Et (b), Prn (c), Pri (d), Bun (e), W-C5H11 (f), PhCH2 (g), PhCH2CH 2 (h), 4-MeC6H4 (i), 4-EtC6H 4 (j) and menthyl (k), have been prepared by reaction of C 6F5C=CPh (3) with ROH in the presence of KOH, and characterised by NMR (1H, 13C, 19F) and mass spectroscopy. The single-crystal structures of PhC=CPh·C 6F5C=CC6F5 (1:2), 3 and 4a,c,d,f,g,i have been determined by X-ray diffraction at 120-160 K, and that of 3 also calculated by an ab initio pseudo-potential DFT method. The tolan moiety is nearly planar in each molecule except 4a, which has a Ph/C 6F5 dihedral angle of 25.8°. The R group adopts an out-of-plane orientation except in 4f, where the n-pentyl chain is nearly coplanar with the C6F5 group at the cost of severe distortion of the C(ar)-C(ar)-O angles (which differ by 13.5°). The structures of 1:2, 3 (pseudo-isomorphous with 1:2), 4a, 4g (disordered) and 4i contain stacks of alternating arene and perfluoroarene moieties; 4c and 4d form discrete centrosymmetric dimers with arene/ perfluoroarene overlap, while 4f forms infinite stacks without such overlap. Differential thermal analysis and transmitted polarised light microscopy revealed no liquid-crystalline behaviour of 3 and 4.",
author = "Smith, {Caroline E.} and Smith, {Philip S.} and Thomas, {Rhodri Ll} and Robins, {Edward G.} and Collings, {Jonathan C.} and Chaoyang Dai and Scott, {Andrew J.} and Simon Borwick and Batsanov, {Andrei S.} and Watt, {Stephen W.} and Clark, {Stewart J.} and Christopher Viney and Howard, {J. A K} and Clegg William and Marder, {Todd B.}",
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Smith, CE, Smith, PS, Thomas, RL, Robins, EG, Collings, JC, Dai, C, Scott, AJ, Borwick, S, Batsanov, AS, Watt, SW, Clark, SJ, Viney, C, Howard, JAK, William, C & Marder, TB 2004, 'Arene-perfluoroarene interactions in crystal engineering: Structural preferences in polyfluorinated tolans', Journal of Materials Chemistry, vol. 14, no. 3, pp. 413-420.

Arene-perfluoroarene interactions in crystal engineering : Structural preferences in polyfluorinated tolans. / Smith, Caroline E.; Smith, Philip S.; Thomas, Rhodri Ll; Robins, Edward G.; Collings, Jonathan C.; Dai, Chaoyang; Scott, Andrew J.; Borwick, Simon; Batsanov, Andrei S.; Watt, Stephen W.; Clark, Stewart J.; Viney, Christopher; Howard, J. A K; William, Clegg; Marder, Todd B.

In: Journal of Materials Chemistry, Vol. 14, No. 3, 07.02.2004, p. 413-420.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Arene-perfluoroarene interactions in crystal engineering

T2 - Structural preferences in polyfluorinated tolans

AU - Smith, Caroline E.

AU - Smith, Philip S.

AU - Thomas, Rhodri Ll

AU - Robins, Edward G.

AU - Collings, Jonathan C.

AU - Dai, Chaoyang

AU - Scott, Andrew J.

AU - Borwick, Simon

AU - Batsanov, Andrei S.

AU - Watt, Stephen W.

AU - Clark, Stewart J.

AU - Viney, Christopher

AU - Howard, J. A K

AU - William, Clegg

AU - Marder, Todd B.

PY - 2004/2/7

Y1 - 2004/2/7

N2 - The compounds 4-ROC6F4C=Ph (4) where R = Me (a), Et (b), Prn (c), Pri (d), Bun (e), W-C5H11 (f), PhCH2 (g), PhCH2CH 2 (h), 4-MeC6H4 (i), 4-EtC6H 4 (j) and menthyl (k), have been prepared by reaction of C 6F5C=CPh (3) with ROH in the presence of KOH, and characterised by NMR (1H, 13C, 19F) and mass spectroscopy. The single-crystal structures of PhC=CPh·C 6F5C=CC6F5 (1:2), 3 and 4a,c,d,f,g,i have been determined by X-ray diffraction at 120-160 K, and that of 3 also calculated by an ab initio pseudo-potential DFT method. The tolan moiety is nearly planar in each molecule except 4a, which has a Ph/C 6F5 dihedral angle of 25.8°. The R group adopts an out-of-plane orientation except in 4f, where the n-pentyl chain is nearly coplanar with the C6F5 group at the cost of severe distortion of the C(ar)-C(ar)-O angles (which differ by 13.5°). The structures of 1:2, 3 (pseudo-isomorphous with 1:2), 4a, 4g (disordered) and 4i contain stacks of alternating arene and perfluoroarene moieties; 4c and 4d form discrete centrosymmetric dimers with arene/ perfluoroarene overlap, while 4f forms infinite stacks without such overlap. Differential thermal analysis and transmitted polarised light microscopy revealed no liquid-crystalline behaviour of 3 and 4.

AB - The compounds 4-ROC6F4C=Ph (4) where R = Me (a), Et (b), Prn (c), Pri (d), Bun (e), W-C5H11 (f), PhCH2 (g), PhCH2CH 2 (h), 4-MeC6H4 (i), 4-EtC6H 4 (j) and menthyl (k), have been prepared by reaction of C 6F5C=CPh (3) with ROH in the presence of KOH, and characterised by NMR (1H, 13C, 19F) and mass spectroscopy. The single-crystal structures of PhC=CPh·C 6F5C=CC6F5 (1:2), 3 and 4a,c,d,f,g,i have been determined by X-ray diffraction at 120-160 K, and that of 3 also calculated by an ab initio pseudo-potential DFT method. The tolan moiety is nearly planar in each molecule except 4a, which has a Ph/C 6F5 dihedral angle of 25.8°. The R group adopts an out-of-plane orientation except in 4f, where the n-pentyl chain is nearly coplanar with the C6F5 group at the cost of severe distortion of the C(ar)-C(ar)-O angles (which differ by 13.5°). The structures of 1:2, 3 (pseudo-isomorphous with 1:2), 4a, 4g (disordered) and 4i contain stacks of alternating arene and perfluoroarene moieties; 4c and 4d form discrete centrosymmetric dimers with arene/ perfluoroarene overlap, while 4f forms infinite stacks without such overlap. Differential thermal analysis and transmitted polarised light microscopy revealed no liquid-crystalline behaviour of 3 and 4.

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M3 - Article

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JO - Journal of Materials Chemistry

JF - Journal of Materials Chemistry

SN - 0959-9428

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Smith CE, Smith PS, Thomas RL, Robins EG, Collings JC, Dai C et al. Arene-perfluoroarene interactions in crystal engineering: Structural preferences in polyfluorinated tolans. Journal of Materials Chemistry. 2004 Feb 7;14(3):413-420.