Singlet Oxygen Responsive Molecular Receptor to Modulate Atropisomerism and Cation Binding.

In switchable molecular recognition, 1 O2 stimulus responsive receptors offer a unique structural change that is rarely exploited. The employed [4+2] reaction between 1 O2 and anthracene derivatives is quantitative, reversible and easily implemented. To evaluate the full potential of this new stimulus, a non-macrocyclic anthracene-based host was designed for the modular binding of cations. The structural investigation showed that 1 O2 controlled the atropisomerism in an on/off fashion within the pair of hosts. The binding studies revealed higher association constants for the endoperoxide receptor compared to the parent anthracene, due to a more favoured preorganization of the recognition site. The fatigue of the 1 O2 switchable hosts and their complexes was monitored over five cycles of cycloaddition/cycloreversion.

Reversible photocapture of a [2]rotaxane harnessing a barbiturate template.

Photoirradiation of a hydrogen-bonded molecular complex comprising acyclic components, namely, a stoppered thread (1) with a central barbiturate motif and an optimized doubly anthracene-terminated acyclic Hamilton-like receptor (2b), leads to an interlocked architecture, which was isolated and fully characterized. The sole isolated interlocked photoproduct (Φ = 0.06) is a [2]rotaxane, with the dimerized anthracenes assuming a head-to-tail geometry, as evidenced by NMR spectroscopy and consistent with molecular modeling (PM6). A different behavior was observed on irradiating homologous molecular complexes 1⊂2a, 1⊂2b, and 1⊂2c, where the spacers of 2a, 2b, and 2c incorporated 3, 6, and 9 methylene units, respectively. While no evidence of interlocked structure formation was observed following irradiation of 1⊂2a, a kinetically labile rotaxane was obtained on irradiating the complex 1⊂2c, and ring slippage was revealed. A more stable [2]rotaxane was formed on irradiating 1⊂2b, whose capture is found to be fully reversible upon heating, thereby resetting the system, with some fatigue (38%) after four irradiation­thermal reversion cycles.

Formation of a hydrogen-bonded barbiturate [2]-rotaxane.

Interlocked structures containing the classic Hamilton barbiturate binding motif comprising two 2,6-diamidopyridine units are reported for the first time. Stable [2]-rotaxanes can be accessed either through hydrogen-bonded preorganization by a barbiturate thread followed by a Cu(+)-catalyzed "click" stoppering reaction or by a Cu(2+)-mediated Glaser homocoupling reaction.

α-Halogenoacetanilides as hydrogen-bonding organocatalysts that activate carbonyl bonds: fluorine versus chlorine and bromine.

α-Halogenoacetanilides (X=F, Cl, Br) were examined as H-bonding organocatalysts designed for the double activation of CO bonds through NH and CH donor groups. Depending on the halide substituents, the double H-bond involved a nonconventional CH⋅⋅⋅O interaction with either a HCXn (n=1-2, X=Cl, Br) or a HCAr bond (X=F), as shown in the solid-state crystal structures and by molecular modeling. In addition, the catalytic properties of α-halogenoacetanilides were evaluated in the ring-opening polymerization of lactide, in the presence of a tertiary amine as cocatalyst. The α-dichloro- and α-dibromoacetanilides containing electron-deficient aromatic groups afforded the most attractive double H-bonding properties towards CO bonds, with a NH⋅⋅⋅O⋅⋅⋅HCX2 interaction.

Anthracene photodimerization in a bis-chromophoric hydrogen-bonding receptor.

The photochemistry and photophysics of a bis-anthracenyl hydrogen-bonding receptor (7-(3,5-bis((6-(4-(anthracen-9-yloxy) butanamido)pyridin-2-yl)carbamoyl)phenylhept-6-ynoate, 2) were investigated in a fluid solution. At room temperature, fluorescence and intersystem crossing compete with intramolecular dimerization to form head-to-head and head-to-tail photoproducts, whereas fluorescence is the principal deactivation pathway at low temperature. Time-resolved fluorescence spectroscopy evidences two excimer-like emitting states whose sensitivity to quenching by oxygen is considerably lower than that of intramolecular photodimerization (K(SV) = ca. 450 vs. <100 L mol(-1), respectively). Based on the temperature-dependence and quenching efficiency of photodimerization, a mechanism is proposed in which the ground-state conformation of the tether controls the formation of the HH vs. HT photodimers via a non-emissive intermediate.

Structural relationships in 2,3-bis-n-decyloxyanthracene and 12-hydroxystearic acid molecular gels and aerogels processed in supercritical CO(2).

Supercritical carbon dioxide is used to prepare aerogels of two reference molecular organogelators, 2,3-bis-n-decyloxyanthracene (DDOA) (luminescent molecule) and 12-hydroxystearic acid (HSA). Electron microscopy reveals the fibrillar morphology of the aggregates generated by the protocol. SAXS and SANS measurements show that DDOA aerogels are crystalline materials exhibiting three morphs: (1) arrangements of the crystalline solid (2D p6m), (2) a second hexagonal morph slightly more compact, and (3) a packing specific of the fibers in the gel. Aggregates specific of the aerogel (volume fraction being typically phi approximately 0.60) are developed over larger distances (approximately 1000 A) and bear fewer defaults and residual strains than aggregates in the crystalline and gel phases. Porod, Scherrer and Debye-Bueche analyses of the scattering data have been performed. The first five diffraction peaks show small variations in position and intensity assigned to the variation of the number of fibers and their degree of vicinity within hexagonal bundles of the related SAFIN according to the Oster model. Conclusions are supported by the guidelines offered by the analysis of the situation in HSA aerogels for which the diffraction pattern can be described by two coexisting lamellar-like arrangements. The porosity of the aerogel, as measured by its specific surface extracted from the scattering invariant analysis, is only 1.8 times less than that of the swollen gel and is characteristic of a very porous material.

(Thio)Amidoindoles and (thio)amidobenzimidazoles: an investigation of their hydrogen-bonding and organocatalytic properties in the ring-opening polymerization of lactide.

The mechanism of the ring-opening polymerization (ROP) of lactide catalyzed by two partner hydrogen-bonding organocatalysts was explored. New amidoindoles 4 a,c, thioamidoindoles 4 b,d, amidobenzimidazoles 5 a,c, and thioamidobenzimidazoles 5 b,c were synthesized and used as activators of the monomer. In the solid state and in solution, compounds 4 and 5 showed a propensity for self-association, which was evaluated. (Thio)Amides 4 and 5 do catalyze the ROP of lactide in the presence of a cocatalyst, tertiary amine 3 a or 3 b, which activates the growing polymer chain through hydrogen-bonding. Reactions were conducted in 2-24 h at 20 degrees C; conversion yields ranged between 22 and 100 %. A detailed study of the intermolecular interactions undertaken between the participating species showed that, as expected, simultaneous weak hydrogen bonds do exist to activate the reagents. Moreover, interactions have been revealed between the partner catalysts 4/5+3. ROP catalyzed by these partner activators is thus governed by multiple dynamic equilibria. The latter should be judiciously adjusted to fine-tune the catalytic properties of (thio)amides and organocatalysts, more generally.

Ring-opening polymerization of L-lactide efficiently triggered by an amido-indole. X-ray structure of a complex between L-lactide and the hydrogen-bonding organocatalyst.

N-(3,5-Bis(trifluoromethyl)phenyl)-1H-indole-2-carboxamide 1e is an efficient hydrogen-bonding organocatalyst for the ring-opening polymerization of l-lactide. This new catalytic species does control the dispersity (1.08) and molecular weight (3460 g/mol vs 3064 in theory) of the poly(l-lactides) prepared in 2 h. (1)H NMR analysis showed that compound 1e complexes l-lactide in CDCl(3) through the two available NH groups (amide and indole). In particular, the catalytic species appeared to be mainly the H-bonding donor amide (1e in extended conformation, alone or dimer (1e)(2)) and, to a lesser extend, the dual H-bonding amido-indole (1e in its the pinched conformation). The first X-ray structure of the complex between a H-bonding organocatalyst and l-lactide also revealed a tight H-bonded network between the dimer (1e)(2) and l-lactide.

Reversible intramolecular photocycloaddition of a bis(9-anthrylbutadienyl)paracyclophane--an inverse photochromic system. (Photoactive cyclophanes 5).

The title compound, 4,13-bis[(1E,3E)-4-(9-anthracenyl)buta-1,3-dienyl][2.2]paracyclophane (2), prepared in 35% overall yield from [2.2]paracyclophane, absorbs light at lambda(max) = 400 nm with a tail down to 480 nm. By irradiation into this band, 2 generates a single photoproduct, 4, whose absorption maximum is situated at 306 nm. The starting material is recovered by irradiation at 306 nm or by heating. This 'inverse' photochromic system has a potential for optical information storage, compound 4 being stable in visible light, at ambient temperature.

Striking correlation between the unusual trigonal crystal packing and the ability to self-assemble into nanofibers of 2,3-di-n-alkyloxyanthracenes.

The space group of the crystals of derivatives of 2,3-dialkoxyanthracenes is monoclinic P2(1)/a (herringbone structure) with the linear ethyl or propyl chains but abruptly changes to the trigonal P3 or R3 space group for butyl to heptyl chains. Strikingly, this switch is correlated with the capacity of these compounds to self-assemble into nanofibers and organogels. Besides, compounds with a chain length exceeding seven carbon atoms could not be crystallized in accordance with the analysis of the projected crystal structure but are nevertheless excellent organogelators. The study of this series of compounds suggests a tight link between the molecular structure of the crystals and that of the organogels.

2,3-Diethoxy-9,10-anthraquinone.

Anthraquinone derivatives form an important class of dyes and are also known for their medicinal properties. Recently, 2,3-disubstituted anthraquinones have been shown unexpectedly to jellify various organic solvents. No information on the packing mode of these derivatives was known. Here, the first X-ray structure of a 2,3-disubstituted anthraquinone is reported, namely 2,3-diethoxy-9,10-anthraquinone, C(18)H(16)O(4). The merit of this study lies in the observation of significant differences between the packing in 9,10-anthraquinone, which displays a herring-bone arrangement, and that in the title 2,3-diethoxy derivative, in which the molecules lie on parallel crystallographic morror planes separated by a distance of 3.4081 (1) A, reminiscent of the graphite layer architecture.

Alkynyl ruthenium colorimetric sensors: optimizing the selectivity toward fluoride anion.

We report on the synthesis of alkynyl ruthenium colorimetric sensors whose receptors are constituted by thiazolidinedione, rhodanine, or barbituric heads as recognition centers for anions. As modifications in the charge density at these recognition centers affect the whole molecule, through the alkynyl ligand acting as a communicating wire, the effects of hydrogen-bonding interactions with the anions were observed with the naked eye and monitored by UV-vis absorption spectrometry. The selectivity of the sensors was improved through electronic modifications of the alkynyl ruthenium subunit: the higher the electron density at the receptor head, the higher the selectivity is. TD-DFT calculations rationalize the long-range electronic communication as a main characteristic of the alkynyl ruthenium species and as a key to improve the selectivity of alkynyl ruthenium-based sensors toward anions.

Detection of a single DNA base-pair mismatch using an anthracene-tagged fluorescent probe.

A novel anthracene-tagged oligonucleotide can discriminate between a fully-matched DNA target sequence and one with a single mismatching base-pair through a remarkable difference in fluorescence emission intensity upon duplex formation.

Structural effects on the ground and excited-state properties of photoswitchable hydrogen-bonding receptors.

The ground- and excited-state properties of a series of photochromic barbiturate receptors (N,N'-bis{6-[omega-(anthracen-9-yloxy)alkanoylamino]pyridin-2-yl}-5-t-butyl-isophthalamide, Tn), in which anthracene chromophores are tethered via (CH2)n (n = 1, 3-6) polymethylene linkers to the H-bond receptor moiety, are described. In these systems, the thermally reversible [4pi + 4pi] photodimerization of the anthracenes yields macrocyclic receptors (TnC) that possess significantly reduced affinity toward barbital as compared to their acyclic counterparts. The length of the tether not only determines the overall binding ability of the cyclized receptor but also has a profound influence on the photochemical and photophysical properties of the anthracene chromophores. The reduced mobility experienced by the covalently bound anthracenes controls the reactivity of a fluorescent excimer that is proposed to be an intermediate in the photocyclization process.

Structural variations in a family of orthodialkoxyarenes organogelators.

A series of low mass organic gelators (LMOGS) 1 to 6 whose chemical structures have in common an orthodialkoxyarene feature was prepared in order to compare the shape of their fibrillar network as investigated by small-angle neutron scattering (SANS) experiments. All members of the family exhibit a pronounced tendency to bundle formation by merging isolated fibers in extended packets of average diameter >500 A. Variations of the 2D packing symmetry are observed from hexagonal to square orderings with close derivatives of the reference member 2,3-didecyloxyanthracene (DDOA). Networks in which the fraction of isolated fibers is significant enough to allow for their SANS identification are those for 6,7-dichloro-2,3-didecyloxyanthracene (Cl(2)DDOA) and 2,3-dodecyloxy-9,10-anthraquinone (5). For this latter, the monodispersity of the cross-sections (thickness=74 A) is remarkable and the rectangular shape (b/a approximately 0.12) accounts for a merging mechanism into anisotropic bundles (ribbons).

Protective effects of 4-hydroxycinnamic ethyl ester derivatives and related dehydrodimers against oxidation of LDL: radical scavengers or metal chelators?

4-Hydroxycinnamate derivatives are known to be potent protectors against oxidation of low-density lipoproteins (LDL), via a combination of free radical scavenging and transition metal chelation. Through a series of 4-hydroxycinnamic ethyl ester derivatives and related 8-8 dehydrodimers, we have tried to bring out the structural requirements for radical scavenging and cupric ion chelation. We found that the monomeric compounds, except for highly lipophilic tert-butyl derivative 3, exhibited rather low radical scavenging properties. Furthermore, they did not chelate copper but, in contrast, reduced cupric ion to cuprous ion, affording the related 8-8 dehydrodimers, for which they could be considered as precursors in vitro. In the copper-dependent human LDL oxidation in vitro, the cyclic 8-8 dehydrodimer forms behaved essentially as efficient copper chelators, while related noncyclic 8-8 forms, which were found to be the best protectors, mainly acted as radical scavengers.

Energy transfer in self-assembled [N]-acene fibers involving > or =100 donors per acceptor.

Anthracene derivatives self-assemble into fibers with a high molecular order, as is evidenced by probing the structure with energy-trapping tetracene analogues. Efficient energy transfer processes involving tens to hundreds of donors per acceptor and high emission quantum yields are outstanding characteristics displayed in these self-assembled fibers.

Naked eye detection of anions by alkynyl-ruthenium exo-receptors: selective recognition of fluoride anion.

Alkynyl-ruthenium complexes bearing terminal hydrogen-bonding receptors act as efficient anion sensors exhibiting large guest-induced colour changes and show unexpectedly high selectivity to fluoride ions.

Synthesis of 2,3-substituted tetracenes and evaluation of their self-assembling properties in organic solvents.

[structure: see text] Rod-shaped 2,3-di-alkoxytetracenes, soluble in common organic solvents, have been synthesized and studied for their gelling ability in organic solvents and their unusual UV-visible spectroscopic properties.