ChemComm
Page 4 of 4
4
a) M. Alaasar, M. Prehm, M. Nagaraj, J. K.Vij and C. Tschierske,
Adv. Mater., 2013, 25, 2186; b) M. Alaasar, M. Prehm, K. May, A.
means that the cubic I432 phase is metastable below 187 °C, but
once formed seems to be persistent. The transition Ia3¯d-I432
observed in the series ABn on chain elongation and with rising
temperature (AB8) is in line with the recently proposed helical
model, as the effective chain volume increases with rising
temperature and growing alkyl chain length and this reduces the
helical pitch becoming incompatible with the Ia¯3d structure and
leading to formation of the I432 cubic phase.10
Eremin and C. Tschierske, Adv. Funct. Mater., 2014, 24, 1703.
DOI: 10.1039/C6CC08226B
5
6
V. Görtz, Liq. Cryst. Today, 2010, 19, 37.
D. Chen, J. H. Porada, J. B. Hooper, A. Klittnick, Y. Shen, M. R.
Tuchband, E. Körblova, D. Bedrov, D. M. Walba, M. A. Glaser, J. E.
Maclennan and N. A. Clark, Proc. Nat. Acad. Sci., 2013, 110, 15931.
a) V. Borshch, Y.-K. Kim, J. Xiang, M. Gao, A. Jakli, V. P. Panov, J.
K. Vij, C. T. Imrie, M. G. Tamba, G. H. Mehl and O. D.
Lavrentovich, Nature Commun., 2013, 4, 2635; b) M. Cestari, S.
Diez-Berart, D. A. Dunmur, A. Ferrarini, M. R. de la Fuente, D. J. B.
Jackson, D. O. Lopez, G. R. Luckhurst, M. A. Perez-Jubindo, R. M.
Richardson, J. Salud, B. A. Timimi and H. Zimmermann, Phys. Rev.
E, 2011, 84, 031704; c) R. J. Mandle, Soft Matter, 2016, 12, 7883.
R. J. Mandle and J. W. Goodby, ChemPhysChem, 2016, 17, 967; Y.
Wang, Z. Zheng, H. K. Bisoyi, K. G. Gutierrez-Cuevas, L. Wang, R.
S. Zolab and Q. Li, Mater. Horiz., 2016, 3, 442.
5
7
In summary, we report herein the design and synthesis of the
10 first examples of hydrogen bonded supramolecular complexes
with polycatenar structure showing dynamic mirror-symmetry
breaking by chirality synchronization in a liquid conglomerate
8
9
[
(Iso1 *]) at the liquid-liquid transition as well as in chiral “Im3¯m-
type” cubic phases (Cub[*]/I432). The liquid conglomerate is
15 obviously only formed if the alkyl chains are short and nano-
segregation between alkyl chain and core unit is sufficiently weak
to prevent formation of a long range cubic lattice. Overall, this
work could initiate further work on using hydrogen bonding for
symmetry breaking in fluids. Moreover, the possibilities provided
20 by the photosensitive azobenzene units23 could lead to interesting
perspectives for chirality switching and phase modulation by
interaction with non-polarized and (linear or circular) polarized
light.24
G. Ungar, V. Percec and M. Zuber, Macromolecules, 1992, 25, 75.
10 C. Dressel, F. Liu, M. Prehm, X. Zeng, G. Ungar and C. Tschierske,
Angew. Chem. Int. Ed., 2014, 53, 13115.
11 a) C. Dressel, T. Reppe, M. Prehm, M. Brautzsch and C. Tschierske,
Nature Chem., 2014, 6, 971; b) M. Alaasar, M. Prehm, Y. Cao, F. Liu
and C. Tschierske, Angew. Chem. Int. Ed., 2016, 55, 312; c) C.
Dressel, W. Weissflog and C. Tschierske, Chem. Commun., 2015, 51,
15850.
12 W. Weissflog, In Handbook of Liquid Crystals: J. W. Goodby, P. J.
Collings, T. Kato, C. Tschierske, H. Gleeson and P. Raynes, Eds.,
Wiley-VCH: Weinheim, 2014, Vol 5, 89.
13 T. Kato and J. M. J. Frechet, J. Am. Chem. Soc., 1989, 111, 8533.
14 B. Friot, D. Boyd, K. Willis, B. Donnio, G. Ungar and D. W. Bruce,
Liq. Cryst., 2000, 27, 605.
Acknowledgement
15 a) C. M. Paleos and D. Tsiourvas, Liq. Cryst., 2001, 28, 1127; b) T.
Kato and Y. Kamikawa, In Handbook of Liquid Crystals: J. W.
Goodby, P. J. Collings, T. Kato, C. Tschierske, H. Gleeson and P.
Raynes, Eds., Wiley-VCH: Weinheim, 2014, Vol. 5, 513.
16 S. M. Jansze, A. Martinez-Felipe, J. M. D. Storey, A. T. M. Marcelis
and C. T. Imrie, Angew. Chem. Int. Ed., 2015, 54, 643.
17 a) G.W. Gray, B. Jones and F. Marson, J. Chem. Soc., 1957, 393; b)
D. Demus, G. Kunicke, J. Neelsen and H. Sackmann, Z. Naturforsch.
A, 1968, 23, 84; c) S. Kutsumizu, Isr. J. Chem., 2012, 52, 844.
18 a) E. Nishikawa and E. T. Samulski, Liq. Cryst., 2000, 27, 1463; b)
E. Nishikawa, J. Yamamoto and H. Yokoyama, Liq. Cryst. 2003, 30,
785.
19 a) J. Mamiya, A. Yoshitake, M. Kondo, Y. Yu and T. Ikeda, J.
Mater. Chem., 2008, 18, 63; b) K. Aoki, M. Nakagawa and K.
Ichimura, J. Am. Chem. Soc., 2000, 122, 10997; c) M. Pfletscher, C.
Wölper, J. S. Gutmann, M. Mezger and M. Giese, Chem. Commun.,
2016, 52, 8549.
25 The work was funded by the DFG (Grant Ts 39/24-1) and the
National Natural Science Foundation of China (No. 21374086).
We thank Beamline BL16B1 at SSRF (Shanghai Synchrotron
Radiation Facility, China) for providing the beamtimes.
Notes and references
30 a Institute of Chemistry, Martin-Luther University Halle-Wittenberg,
Kurt-Mothes Str.2, D-06120 Halle/Saale, Germany.
E-mail: carsten.tschierske@chemie.uni-halle
b Department of Chemistry, Faculty of Science, Cairo University, Giza,
Egypt. E-mail: malaasar@sci.cu.edu.eg
35 c State Key Laboratory for Mechanical Behavior of Materials,
Xi’an Jiaotong University, Xi’an 710049, P. R. China.
E-mail: feng.liu@xjtu.edu.cn
† Electronic Supplementary Information (ESI) available: [Synthesis,
analytical data, additional data]. See DOI: 10.1039/b000000x/.
40 ‡ In contrast to discrete hydrogen bonded complexes, multiple
cooperative hydrogen bonding between amphiphilc glycerol-based or
carbohydrate based molecules forming polymeric hydrogen bonding
networks are more common.25
20 a) W. Zhou, T. Kobayashi, H. Zhu and H. F. Yu, Chem. Commun.,
2011, 47, 12768; b) Y. J. Chen, H. F. Yu, L. Y. Zhang, H. Yang and
Y. F. Lu, Chem. Commun., 2014, 50, 9647.
21 K. Saito, Y. Yamamura, Y. Miwa and S. Kutsumizu, Phys. Chem.
Chem. Phys., 2016, 18, 3280.
§ Mirror symmetry breaking induced by hydrogen bonding in soft matter
45 was previously only reported for the NTB phases of hydrogen bonded
mesogenic trimers.24
¶ The azopyridine derivatives Bn have previously been used for the
formation of supramolecular self-assembled hydrogen bonded19 and
halogen-bonded LCs20 with light induced phase transitions.
50
22 G. Pescitelli, L. Di Bari and N. Berova, Chem. Soc. Rev. 2014. 43,
5211.
23 H. M. D. Bandara and S. C. Burdette, Chem. Soc. Rev. 2012, 41,
1809.
24 D. A. Paterson, J. Xiang, G. Singh, R. Walker, D. M. Agra-
Kooijman, A. Martınez-Felipe, M Gao, J. M. D. Storey, S. Kumar, O.
D. Lavrentovich and C. T. Imrie, J. Am. Chem. Soc., 2016, 138,
5283.
25 K. Borisch, S. Diele, P. Göring, H. Kresse and C. Tschierske, Angew.
Chem. Int. Ed., 1997, 36, 2087.
1
2
C. Tschierske and G. Ungar, ChemPhysChem, 2016, 17, 9.
a) J. Thisayukta, Y. Nakayama, S. Kawauchi, H. Takezoe and J.
Watanabe, J. Am. Chem. Soc., 2000, 122, 7441; b) G. Dantlgraber, A.
Eremin, S. Diele, A. Hauser, H. Kresse, G. Pelzl and C. Tschierske,
Angew. Chem. Int. Ed., 2002, 41, 2408; c) L. E. Hough, M. Spannuth,
M. Nakata, D. A. Coleman, C. D. Jones, G. Dantlgraber, C.
Tschierske, J. Watanabe, E. Körblova, D. M. Walba, J. E.
Maclennan, M. A. Glaser and N. A. Clark, Science, 2009, 325, 452;
H. Sasaki, Y. Takanishi, J. Yamamoto and A. Yoshizawa, J. Phys.
Chem. B, 2015, 119, 4531.
3
H. Takezoe, Top. Curr. Chem., 2012, 318, 303.
4
| Journal Name, [year], [vol], 00–00
This journal is © The Royal Society of Chemistry [year]