You are on page 1of 4


a process in the case of two-site (ditopic) complementary components TE, and T3,. The resulting supramolecular polymeric material (TE,, T32)nmay present liquid crystalline properties if suitable chains are introduced onto the components. We now describe results obtained along these lines in the case where T is a group derived from tartaric acid and the complementary units E, 3 are of uracil (U) and 2,6-diacylamino-pyridine (P) type. The formation of triply hydrogenbonded complementary pairs by these units is well documentedF3 and has been used in separation procedures[41 in macrocyclic receptor molecules ['I and for inducing the appearance of supramolecular mesophases."] The tartaric acid (T) unit provides in addition the opportunity to investigate the effect of changes in chirality on the properties of the species formed. The required components LP,, LU,, DP,, MP, and MU, derived from L( +), D( -) and meso (M) tartaric acid respectively, have been synthesized in a straightforward fashion. Alkylation of the L( + )-N,N,NN-tetramethyltartramide L-lL6] by treatment with NaH in DMF followed by C,,H,,OTS[~~ gave the bis-ether L-2 (80%; mp < 50C; a ] : ' = + 45", c = 0.1, CHCl,), which was hyfrom hexane; [ drolyzed with aqueous HCI (25 %) at reflux[*] to the diacid L-3 (65 YO; mp 76 "C; from hexane; [a];5= + 14.7", c = 0.9, CHC1,). Treatment of L-3 with PCI, in CH,C1, (18 h, rt)['] gave the corresponding bis-acid chloride which by reaction with 6-hydroxymethyl uracil['] (in HMPA) and with 2,6-diacetylamino-4-(hydroxyethyl)oxy-pyridine~101 (in DMF) in the presence of 4-dimethylaminopyridine (2 eq.; 2 h; rt) afforded respectively the desired compounds LU, (50 %, [a];5= 37", c = 0.5, THF) and LP, (27%; [a];' = + 25.5", c = 0.5, THF) after purification by chromatography and crystallization from THF and aqueous ethanol respectively. Following the same reaction sequence D( -) tara ] ; '= - 25.4", c = 0.5, THF). taric acid gave DP, (23 %; [

Molecular Recognition Directed Self-Assembly of Supramolecular Liquid Crystalline Polymers from Complementary Chiral Components
By Claudine Fouquey, Jean-Marie Lehn,* and Anne-Marie Levelut Recognition processes occuring at the molecular level may lead to changes at the level of the material, thus expressing molecular information on the macroscopic scale. This is the case namely when the formation of a complementary supramolecular pair E 3 induces the appearance of a liquid crystalline phase.''] If two (or more) units E or 3 are grafted onto a template T, mixing TE, with the complementary T3,,, may lead to the self-assembly of a linear or cross-linked polymeric supramolecular species (TE, ,T3,,,)" whose existence is conditioned by the molecular recognition directed association between the E and 3 groups.[21 Figure I represents schematically such

RCOCH(OR)CH(OR)COR' 1 R = H, R = N(CH,), 2 R = C,,H,,, R' = N(CH3), 3 R = C,,H,,, R' = OH


Fig. 1, Schematic representation of the formation of a polymeric supramolecular species (TE,, T3,)" by association of two complementary ditopic components TE, and T3,.


Prof. .I.-M. Lehn, Dr. C . Fouquey Chimie des Interactions MolC.culaires Collkge de France 11, Place Marcelin Berthelot, F-75005 Paris (France)

Dr. A.-M. Leveht Laboratoire de Physique des Solides, Universite Paris-Sud F-91405 Orsay Cedex (France)

[**I 254

We thank Dr. Frunpise Livulunt for discussion of the optical textures.

The corresponding compounds derived from meso-tartaric acid were obtained in a similar way from meso-N,N,N,Ntetrdmethykartramide (mp 194 "C) via M-2 (51 %; mp 79C; from hexane), M-3 (95%; mp 84-88'; from hexane) and the meso-bis-acid chloride, giving MU, (33 %); and MP, (36%). All new compounds had spectral (NMR, mass) and microanalytical properties in agreement with their structure. The substances LP, , LU,, DP, , MP, and MU, contain two heterocyclic units capable of undergoing association via
0935-9648/90/0505-02S4 $02.50/0 Adv. Muter. 2 (1990) No. 5


Verlugsgeseilschaft mhH. 0-6940 Weinheim,1990



hydrogen bonding in a way reminiscent of nucleic base pairing.[' '] Indeed, 131 mixtures of the complementary pairs (LP, LU,) and (MP, MU,) yielded definite compounds, different from their components, in the solvent free state as well as in solution. In d,-THF they showed downfield shifts (of about 0.2-0.3 ppm for the L mixture) for the NH 'H-NMR signals with respect to the pure substances, as expected [', 4, 'I if association occurs.["] Marked changes appeared likewise in the circular dichroism spectra of (LP, + LU,). The change of sign and large increase in intensity observed on going from THF ( A E , , = ~ -1.4; = +4.0cm-'M-') to ethanol = -100; A C ,= ~~ 45 cm-'M-') solution may be related to aggregate formation due to low solubility in ethanol. Similar changes were reported for mesophases of polynucleotide~.['~I Of particular interest are the phase transition properties of these materials and their mixtures. The thermal and optical properties have been studied by differential scanning microcalorimetry and with a polarizing microscope. The temperatures and enthalpies of transition determined are listed in Table 1. It is seen that the pure compounds are solids pre-

Table 1. Temperatures and enthalpies of transition for compounds LU,, LP,, MU,, MP, and their 131 mixtures[a]. Material Transition T ["Cl K 216-220 I K 29;45; 58 1 K < 25 M 254 I K 25-33; 43-54 I K < 25 M 242-244 I K 190-193 I K 109-115 I K < 25 M 219-222 I

LU, LP2 (LU* + LPd DP2 (DPz + LUz) MU2 MP2 (MU, + MPz)

AH [kcal mol-I] 11 3 35 (M -1) 3.5 33 (polymorphic) 8.2 22.5

[a] Measurements performed with a Perkin-Elmer DSC2 microcalorimeter. K: crystalline phase; M: mesomorphic phase; I: isotropic phase. The mixtures were obtained from l j l solutions of the components in THF after thorough evaporation to dryness so as to remove all solvent.

senting more or less complex melting behavior due to solidstate polymorphism. In contrast, the 131 mixtures (LP, + LU,), (DP, + LU,) and (MP, + MU,) present a thermotropic rnesophase from below room temperature to above 200 "C. The material has the aspect of a highly birefringent glue that forms fibers on spreading. With solvents such as THF, dioxane, CHCI, etc. gels are obtained. Figure 2 shows several aspects of the optical textures observed for these 1/1 mixtures under different conditions. It is seen that the LL and MM mixtures are clearly different. In the LL mixture as a gel, the presence of stretched and helically wound fibers is clearly seen. Some textures resemble those of DNA fibers, with sinusoidal or helical arrangements. As the solvent evaporates, patterns appear that are similar to the banded structures described for oriented thermotropic polymers (such as Kevlar or hydroxypropylcellulose['41).[**1
Adv. Muter. 2 (1990) No. 5

Fig. 2. Optical textures observed for different preparations between crossed polarizers; (LU,, LP,). mixtures (top and center), (MU,, MP,), mixture (bottom).

It is reasonable to assume that the complementary units will form the expected triply hydrogen bonded pairs,[' - 'I so that the entirely different behavior of the pure compounds and of the 131mixtures may be attributed to the spontaneous association of the complementary components into a polycondensate based on hydrogen bonding. The overall process may then be described as the self-assembly of a supramolecular liquid crystalline polymer based on molecular recognition between complementary components. The resulting species (LP,, LU,), is represented schematically by structure A.

0 VCH Verlagsgesellschaft mbH, 0-6940

Weinheim. 1990

093s-9648~9OiOSOS-0255 $02.50/0







The spontaneous formation of microstructures from different types of components has been reported, for instance helical fibers from guanine nucleosides," lyomesophases from diguanosine phosphates," 61 helical and tubular structures from polymerizable lecithins," 71 helical superstructures and fibers in lipid bilayers from chiral components,['*. and superhelical strands from phospholipid-nucleoside conjugates.["] Molecular recognition affects the properties of molecular layers[z1* "1 and electron donor-acceptor interactions may induce me so phase^.[^^^ The X-ray patterns of the viscous LL, DL and MM mixtures indicate that they are hexagonal columnar mesophases. The diameter of the columns is nearly the same for the three systems: 37 A. A tentative description of the supramolecular organization is derived from X-ray diffraction data obtained with more or less aligned samples. For the LL mixture, a period of c = 3.45 A along the column axis is indicated; this separation corresponds to the stacking distance between flat heterocyclic groups and is compatible with a picture in which the base pairs are located in parallel planes oriented almost perpendicularly to the axis of the column. Moreover there is evidence that the pairs are arranged in a helicoidal structure with an estimated pitch of C = 12.8 and a mean diameter of 14.7 A. Taking into account the density of the material, our data are consistent with a model in which the columns have a triple helix superstructure, made of three strands resulting from the polyassociation of the two components TP, and TU, in a polymeric fashion. On each strand there are C/c = 3.71 residues per turn (120", since it is a triple helix), each residue being alternatively a (T/2)P.U(T/2) and a (T/2)U.P(T/2) sequence.'241 A schematic representation of the supramolecular structure

is shown in Figure 3 (left). The distance between two successive pairs (UP-PU) or (PU-UP) along a helical strand is about 15 A, which is compatible with the lengths of the UTU and PTP components (in which the spacer groups separating the two heterocyclic bases are somewhat different). For the MM mixture, the main period along the column axis is c = 3.55 8, with a twofold superstructure. The data fit a model built on three polymeric strands in a zigzag arrangement as shown in Figure 3 (right).


Fig. 3. Schematic representation of the columnar superstructures suggested by the X-ray data for (LP,, LU,)., (left) and (MP,, MU,), (right); each spot represents a PU or UP base pair; spots of the same type belong to the same helical strand of the triple helix; the dimensions are compatible with an arrangement of the PTP and UTU components along the strands indicated (see also text); the aliphatic chains stick out of the cylinder, more or less perpendicularly to its axis. For (LP,, LU,). a single helical strand and the full triple helix are respectively represented on the bottom and at the top of the column. For (MP,, MU,)., the representation shown corresponds to the column cut parallel to its axis and flattened out.
093S-9648/90/OSOS-O256 $OZ.SO/O



Verlug.~gesellschafi mbH, 0-6940 Weinheim.1990

Adv. Mater. 2 (1 990) No. 5


[I, 4, 51. This may indicate that the present substances containing two such units undergo autoassociation to some extent. [13] G. B. Lortkipanidze, Yu. M. Evdokimov, A. T. Demho, Ya. M. Varshavskii, Moi. B i d . {Moscow) 18 (1984) 466; Chem. Absir. 100 (1984) 205164m; S. G. Skuridin, G. B. Lortkipdnidze, 0. R. Musaev, Yu. M. Evdokimov, Vysokomol. Soedin., Ser. A 27 (1985) 2266; Chem. Ahstr. 105 (1986) 209302f; Yu. M. Evdokimov, S. G. Skuridin, N. M. Akimenko. ibid. 26 (1984) 2403; Chem. Abstr. 102 (1985) 149691 h. [I41 C. Viney, A. M. Donald, A. H. Windle, J. Muter. Sci. 18 (1983) 1136; A.M. Donald, A. H. Windle. ibid. 18 (1983) 1143; A . M . Donald, C. Viney, A. H. Windle, Polymer 24 (1983) 155; P. Navard, L Polym. Sci., Polym. Phys. Ed. 24 (1986) 435. [I51 P. Tougard, J.-F. Chantot, W Guschlbauer, Biochim. Biophys Acta 308 (1973) 9. [16] G. P. Spada, A. Carcuro, F. P. Colonna, A. Garbesi, G. Gottarelli, Liq. Cryst. 3 (1988) 651; P. Mariani, C. Mazabard, A. Garbesi, G. P. Spada, J. Am. Chem. Soc. 111 (1989) 6369. [I71 J. H. Georger, A. Singh, R. R. Price, J. M. Schnur, P. Yager, P. E. Schoen, J. Am. Chem. SOC.109 (1987) 6169. [IS] N. Nakashima, S . Asakuma, T. Kunitake, J. Am. Chem. Soc. 107 (1985) 509. [I91 J.-H. Fuhrhop, P. Schnieder, E. Boekema, W. Helfrich, J. A m . Chem. SOC. I10 (1988) 2861. [20] H. Yanagawa, Y Ogawa, H. Furuta, K. Tsuno, J. Am. Chem. SOC.11I (1989) 4567; Chem. Left. 1989,403, [21] H. Ringsdorf, B. Schlarh, J. Venzmer, Angew. Chem. Int. Ed. Engl. 27 (1988) 113; Angew. Chem. 100 (1988) 117. [22] E. M. Arnett, N. G. Harvey, P. L. Rose, Acc. Chem. Res. 22 (1989) 131. Jpn. 53 (1980) 3079; H. Rings[23] K. Araya, Y. Matsunga, Bull. Chem. SOC. dorf, R. Wiistefeld, E. Zerta, M. Ebert, J. H. Wendorff, Anxew. Chem. I n t . Ed. Engl. 28 (1989) 914; Angew. Chem. 101 (1989) 934. [24] The X-ray data are rather intensitive to the doubling of the period induced by the differences that actually exist between these two species. A single strand helical model would have a 3.53 8, pitch and 2.78 residues per turn, and is not compatible with the X-ray patterns, which also exclude a dimeric l / l association of two components into a sort of supramolecular cage. [25] For molecular liquid crystalline polymers see: H. Finkelmann, Angew. Chem. Int. Ed. Engl. 26 (1987) 816; Angew. Chem. 99 (1987) 840. [26] For studies on biomesogens, see: S. Hoffmann, W. Witkowski, Am. Chem. Soc. Synip. Ser. 74 (1978) 178; S. Hoffmann. 2. Chem. 27 (1987) 395. 1271 J.-M. Lehn, Angew. Chem. I n t . Ed. Engl. 27 (1988) 89; Angew. Chem. 100 (1988) 91.

The LD mixture presents a mesophase with columns of nearly the same characteristics. There are four residues per turn (120) but each of them has a different conformation inducing a fourfold superstructure in the residue sequence. The fact that these three materials have different structures shows the profound influence of chirality changes on the superstructure formed. The present results indicate that it is possible to engineer molecular components that may form liquid crystalline polym e r ~ [of ~a ~ supramolecular ] nature (or mesomorphic polymolecular associations) by the self-assembly of complementary subunits, thus expressing the recognition process occurring on the molecular level via the formation of a macroscopic mesophase, whose properties may in addition depend on the chirality of the components. They extend supramolecular chemistry [l to the formation of polymeric supermolecules.[21The materials obtained also represent mesophases resulting from a base pairing process of a biological type.[261 Finally, the formation of these supramolecular mesophases by recognition induced self-assembly involves a molecular information dependent process that leads to the generation of intelligent (or informed) supramolecular materials.
Received: December 29, 1989

[I] M.-J. Brienne, J. Gabard, J.-M. Lehn, I. Stibor, J. Chem. Soc. Chem. Commun. 1989, 1868. [2] The term polymer will he used here for designating a repetitive polymolecular association. [3] See for instance: G. Simundza, T. D. Sakore, H. M. Sobell, J. Mol. Biol. 48 (1970) 263; F. E. Scarhrough, H.-S. Shieh, D. Voet, Proc. Nutl. Acad. Sci. USA 73 (1976) 3807. [4] B. Feibush, A. Figueroa, R. Charles, K. D. Onan, P. Feibush, B. L. Larger, J. Am. Chem. Soc. 108, (1986) 3310; B. Feibush, M. Saha, K. Onan, B. Karger, R. Giese, ibid. 109 (1987) 7531. [5] A. D. Hamilton, D. Van Engen, J. Am. Chem. SOC. 109 (1987) 5035; A. D. Hamilton, A. Muehldorf, S.-K. Chang, N. Pant, S. Goswami, D. Van Engen, J. Incl. Phen. Molec. Reco. Chem. 7 (1989) 27, and references therein. [6] D. Seebach, H. 0 . Kalinowski, W. Langer, G. Grass, E. M. Wilka, Org. Synth. 61 (1983) 24. [7] A. Anantanarayan, V. A. Carmichael, P. J. Dutton, T. M. Fyles, M. J. Pitre, Synlh. Commun. 16 (1986) 1771. [8] J.-P. Behr, J.-M. Girodeau, R. C. Hayward, J.-M. Lehn, J.-P. Sauvage, Helv. Chim. Acta 63 (1980) 2096. 191 K. L. Nagpal, J. Med. Chem. 15 (1972) 121. [lo] Prepared in four steps from 4-benzyloxy-2.6-diaminopyridine: diacetylation (Ac,O, pyridine), hydrogenolysis of the benzyl group (H2, Pd/C), alkylation with 2-bromoethylacetate (DMF, K,CO,), saponification (IN NaOHIMeOH). D. G. Markees, V. C. Dewey, G. W. Kidder, J. Med. Chem. I 1 (1968) 126. I l l ] A number of artificial analogues of dinucleotides have been reported, see for instance: D. T. Browne, J. Eisinger, N. J. Leonard, J. Am. Chem. Soc. 90 (1968) 7302; N. J. Leonard, Ace. Chem. Res. 12 (1979) 423; K. Golankiewicz, L. Celewicz, Polish J. Chem. 52 (1978) 1035; 1. Sasaki, M.-N. Dufour, A. Gaudemer, Nouv. J. Chim. 6 (1982) 341; I. Saito, H. Sugiyama, T. Matsuura, K. Fukuyama, Tetrahedron Lett. 1985, 4467; M. S. Kim and G. W. Gokel, J. Chem. Sac. Chem. Commun. 1987,1686; T. Ishida, Y. Tokura, M. Shimamoto, M. Doi, M. Inoue, Chem. Pharni. Bull. Jpn. 35 (1987) 1691; J. L. Sessler, D. Magdal, J. Hugdall, J. Incl. Phen. Mol. Reco. 7 (1989) 19; M. M. Harding, J.-M. Lehn, unpublished results, see in . Witkowski, H. ref. 27; for a polymeric analogue see: S. Hoffmann, W Schuhert, Z. Chem. 14 (1974) 154. [12] Much larger shifts of 1.5-2.0 ppm are found with respect to compounds containing a single U or P unit [I], in line with earlier observations
Adv. Muter. 2 (1990) No. 5

Crystal Synthesis under Langmuir Monolayers **

By Stephen Mann, * Brigid R . Heywood, Sundara Rajam, Justin B. A . Walker, Roger J. Davey, and J. Derek Birchall We are currently exploring the potential of crystal synthesis under Langmuir monomolecular films. Our aims are to determine the nature of the molecular recognition processes at inorganic-organic interfaces and to use chemically designed macromolecular surfaces as model systems for biomineralization and in the crystal engineering of inorganic

[*] Dr. S. Mann, Dr. B. R. Heywood, S. Rajam, J. B. A. Walker

School of Chemistry, University of Bath Bath BA2 7AY (UK) Dr. R. J. Davey ICI plc, Chemicals and Polymers Ltd. Research and Technology Department Runcorn, Cheshire WA7 4QE (UK) Prof. J. D. Birchall ICI Advanced Materials Runcorn, Cheshire WA7 4QE (UK) We thank Mr. J. M . Didymus for assistance with control experiments and Mr. B. Chapman for help with X-ray diffraction measurements. The work was supported by the SERC and ICI plc.


0 VCH Verlagsgesellschaft mbH, 0-6940

Weinheim, 1990

0935-964Xj90j0505-OZ57 $02.5010