Synthesis,Photophysics, and Self‐Assembly of Furan‐Embedded Heteroarenes

A series of pyrene/phenanthrene‐fused furan derivatives ( 1 – 8 ) were synthesized by a simple condensation reaction between pyrene‐4,5‐diketone/phenanthrenequinone and substituted phenol/naphthol in the presence of trifluoromethanesulfonic acid in 1,2‐dichlorobenzene heated at reflux. The formed compounds can emit strong blue light in organic solvents. Additionally, the self‐assembly behaviors of two of the compounds ( 3 and 5 ) were studied through re‐precipitation method and the resulting nanostructures were characterized by UV/Vis, fluorescence spectra, and field‐emission scanning electron microscopy (FESEM). The findings showed that the shape and size of compounds 3 and 5 could be tuned by the ratio of THF and hexadecyl trimethyl ammonium bromide (CTAB) solution in water.     

Photooxidative degradation of dye pollutants accumulated in self-assembled natural polyelectrolyte microshells under visible radiation

A novel route to facilitate the degradation of dye pollutants, a class of well-known recalcitrant organic pollutants, is reported. This new approach is based on a natural polyelectrolyte microshell that was preformed by the alternate adsorption of the anionic alginate sodium (ALG) and the cationic chitosan (CHI) onto weakly cross-linked melamine formaldehyde (MF) colloidal particles, and the subsequent sacrifice of MF templates in 0.1 M HCl. The as-prepared microshells could accumulate rhodamine B (RhB) and fluorescein (Flu) efficiently in water under ordinary conditions by means of a simple mixing process. The photodegradation of the accumulated RhB and Flu was examined in the presence of Fe3+ and H2O2 under visible radiation. The accumulated RhB and Flu are rapidly degraded and the assembled shells maintain their intact spherical shape throughout the photoreaction process. Results of recycling degradation experiments and the photochemical behavior of the shells, as demonstrated by confocal laser scanning microscopy (CLSM), UV-visible spectroscopy, and scanning force microscopy (SFM), further suggest that the constructed shells may be used as environmentally friendly microcontainers for the elimination of dyes in wastewater.     

J-aggregates: from serendipitous discovery to supramolecular engineering of functional dye materials

J-aggregates are of significant interest for organic materials conceived by supramolecular approaches. Their discovery in the 1930s represents one of the most important milestones in dye chemistry as well as the germination of supramolecular chemistry. The intriguing optical properties of J-aggregates (in particular, very narrow red-shifted absorption bands with respect to those of the monomer and their ability to delocalize and migrate excitons) as well as their prospect for applications have motivated scientists to become involved in this field, and numerous contributions have been published. This Review provides an overview on the J-aggregates of a broad variety of dyes (including cyanines, porphyrins, phthalocyanines, and perylene bisimides) created by using supramolecular construction principles, and discusses their optical and photophysical properties as well as their potential applications. Thus, this Review is intended to be of interest to the supramolecular, photochemistry, and materials science communities.     

Structure-property relationships for self-assembled zinc chlorin light-harvesting dye aggregates

A series of zinc 3(1)-hydroxymethyl chlorins 10 a-e and zinc 3(1)-hydroxyethyl chlorins 17 with varied structural features were synthesized by modifying naturally occurring chlorophyll a. Solvent-, temperature-, and concentration-dependent UV/Vis and CD spectroscopic methods as well as microscopic investigations were performed to explore the importance of particular functional groups and steric effects on the self-assembly behavior of these zinc chlorins. Semisynthetic zinc chlorins 10 a-e possess the three functional units relevant for self-assembly found in their natural bacteriochlorophyll (BChl) counterparts, namely, the 3(1)-OH group, a central metal ion, and the 13(1) C==O moiety along the Q(y) axis, and they contain various 17(2)-substituents. Depending on whether the zinc chlorins have 17(2)-hydrophobic or hydrophilic side chains, they self-assemble in nonpolar organic solvents or in aqueous media, respectively. Zinc chlorins possessing at least two long side chains provide soluble self-aggregates that are stable in solution for a prolonged time, thus facilitating elucidation of their properties by optical spectroscopy. The morphology of the zinc chlorin aggregates was elucidated by atomic force microscopy (AFM) studies, revealing well-defined nanoscale rod structures for zinc chlorin 10 b with a height of about 6 nm. It is worth noting that this size is in good accordance with a tubular arrangement of the dyes similar to that observed in their natural BChl counterparts in the light-harvesting chlorosomes of green bacteria. Furthermore, for the epimeric 3(1)-hydroxyethyl zinc chlorins 17 with hydrophobic side chains, the influence of the chirality center at the 3(1)-position on the aggregation behavior was studied in detail by UV/Vis and CD spectroscopy. Unlike zinc chlorins 10, the 3(1)-hydroxyethyl zinc chlorins 17 formed only small oligomers and not higher rod aggregate structures, which can be attributed to the steric effect imposed by the additional methyl group at the 3(1)-position.     

Construction of Helical J‐Aggregates Self‐Assembled from a Thymidylic Acid Appended Anthracene Dye and DNA as a Template

Driven round the twist by DNA : One‐dimensional helical J‐aggregates are formed by the self‐assembly of thymidylic acid appended anthracene dye (shown in red and yellow) in the presence of complementary single‐stranded oligoadenylic acid (shown in green and blue) in an aqueous solution.

     

Photostable, amino reactive and water-soluble fluorescent labels based on sulfonated rhodamine with a rigidized xanthene fragment

Highly water soluble fluorescent dyes were synthesized and transformed into new amino reactive fluorescent labels for biological microscopy. To this end, rhodamine 8 (prepared from 7-hydroxy-1,2,3,4-tetrahydroquinoline (7) and phthalic anhydride in 85 % aq. H(3)PO(4)) was sulfonated with 30 % SO(3) in H(2)SO(4) and afforded the water soluble disulfonic acid 3 a (64 %). Amidation of the carboxy group in 3 a with 2-(methylamino)ethanol in the presence of O-(7-azabenzotriazol-1-yl)-N,N,N',N'-tetramethyluroniumPF(6) (-) (HATU) led to alcohol 3 b (66 %), which was transformed into the amino reactive mixed carbonate 3 d with di(N-succinimidyl)carbonate and Et(3)N. Reaction of the carboxy group in 3 a with MeNH(CH(2))(2)CO(2)Me and N,N,N',N'-tetramethyl-O-(N-succinimidyl)-uroniumBF(4) (-) (TSTU) yielded methyl ester 13. After saponification of the aliphatic carboxy group in 13, the compound was converted into NHS-ester 3 e (using HATU and Et(3)N). Heating of 7 with trimellitic anhydride in H(3)PO(4) gave a mixture of dicarboxylic acids 14 and 15 (1:1). Regioisomer 15 was isolated, sulfonated with 30 % SO(3) in H(2)SO(4), and disulfonic acid 3 f was used for the synthesis of the mono NHS-ester 3 g, in which the sterically unhindered carboxy group was selectively activated (with N-hydroxysuccinimide, HATU, and Et(3)N). The sulfonated rhodamines 3 b, c and f are soluble in water (up to 0.1 M), have excellent photostabilities and large fluorescence quantum yields. Subdiffraction resolution images of tubulin filaments of mammalian cells stained with these dyes illustrate their applicability as labels for stimulated emission depletion microscopy and other fluorescence techniques.     

Self‐Assembly and Aggregate‐Induced Enhanced Emission of Amphiphilic Fluorescence Dyes in Water and in the Solid State

1‐Cyano‐1,2‐bis(biphenyl)ethene (CNBE) derivatives with a hexa(ethylene glycol) group as an amphiphilic side chain were synthesized and the self‐assembling character and fluorescence behavior were investigated. The amphiphilic derivatives showed aggregate‐induced enhanced emission (AIEE) in water and in the solid state. The fluorescence quantum yield increased as the rigidity of the aggregates increased (i.e., in ethyl acetate<in water<in the solid state). As determined from measurements of fluorescence spectra, fluorescence quantum yields, and fluorescence lifetimes, a key factor for the enhanced emission is suppression of the nonradiative decay process arising from restricted molecular motion. Additionally, the difference in the emission rate constant is not negligible and can be used to interpret the difference in fluorescence quantum yield in water and in the solid state.     

Non‐covalent Versus Covalent Control of Self‐Assembly and Chirality of Nile Red‐modified Nucleoside and DNA

A DNA‐based covalent versus a non‐covalent approach is demonstrated to control the optical, chirooptical and higher order structures of Nile red ( Nr ) aggregation. Dynamic light scattering and TEM studies revealed that in aqueous media Nr ‐modified 2′‐deoxyuridine aggregates through the co‐operative effect of various non‐covalent interactions including the hydrogen bonding ability of the nucleoside and sugar moieties and the π‐stacking tendency of the highly hydrophobic dye. This results in the formation of optically active nanovesicles. A left‐handed helically twisted H‐type packing of the dye is observed in the bilayer of the vesicle as evidenced from the optical and chirooptical studies. On the other hand, a left‐handed helically twisted J‐type packing in vesicles was obtained from a non‐polar solvent (toluene). Even though the primary stacking interaction of the dye aggregates transformed from H→J while going from aqueous to non‐polar media, the induced supramolecular chirality of the aggregates remained the same (left‐handed). Circular dichroism studies of DNA that contained several synthetically incorporated and covalently attached Nr ‐modified nucleosides revealed the formation of helically stacked H‐aggregates of Nr but—in comparison to the noncovalent aggregates—an inversed chirality (right‐handed). This self‐assembly propensity difference can, in principle, be applied to other hydrophobic dyes and chromophores and thus open a DNA‐based approach to modulate the primary stacking interactions and supramolecular chirality of dye aggregates.     

Cooperative Supramolecular Polymerization: Comparison of Different Models Applied on the Self‐Assembly of Bis(merocyanine) Dyes

Three new molecular building blocks 1 a – c for supramolecular polymerization are described that feature two dipolar merocyanine dyes tethered by p‐xylylene spacers. Concentration‐ and temperature‐dependent UV/Vis spectroscopy in chloroform combined with dynamic light scattering, capillary viscosimetry and atomic force microscopy investigations were applied to elucidate the mechanistic features of the self‐assembly of these strongly dipolar dyes. Our detailed studies reveal that the self‐assembly is very pronounced for bis(merocyanines) 1 a , b bearing linear alkyl chains, but completely absent for bis(merocyanine) 1 c bearing sterically more bulky ethylhexyl substituents. Both temperature‐ and concentration‐dependent UV/Vis data provide unambiguous evidence for a cooperative self‐assembly process for bis(merocyanines) 1 a , b , which was analyzed in detail by the Meijer–Schenning–Van‐der‐Schoot model (applicable to temperature‐dependent data) and by the Goldstein–Stryer model (applicable to concentration‐dependent data). By combining both methods all parameters of interest to understand the self‐assembly process could be derived, including in particular the nucleus size (8–10 monomeric units), the cooperativity factor (ca. 0.006), and the nucleation and elongation constants of about 10³ and 10⁶ M ^?1 in chloroform at room temperature, respectively.     

Evidence for Kinetic Nucleation in Helical Nanofiber Formation Directed by Chiral Solvent for a Perylene Bisimide Organogelator

The self‐assembly behavior of an achiral perylene bisimide (PBI) organogelator that bears two 3,4,5‐tridodecyloxybenzoylaminoethyl substituents at the imide positions has been investigated in chiral solvents (R)‐ and (S)‐limonene in great detail by circular dichroism (CD) spectroscopy and atomic force microscopy (AFM). CD spectroscopic studies on dilute solutions revealed a preferential population of one‐handed helical assemblies in chiral solvent with an enantiomeric excess close to 100 %, whereas AFM images of more than 100 nanofibers of the organogel obtained from more concentrated solutions were found to consist of both handed helices with an enantiomeric excess of only 20 %. This discrepancy is attributed to the fast gelation process at high dye concentration that evidently proceeds through non‐equilibrated nuclei in a kinetic rather than thermodynamic self‐assembly process. Under these conditions the chiral induction from the homochiral solvent may not be adequate in effectively populating only one‐handed helices.     

The self-ordering properties of novel phthalocyanines with out-of-plane alkyl substituents

Two novel homologous series of phthalocyanines were prepared from 2,2-dialkylindane and 2,2-dialkyl-1,3-benzodioxole precursors. It was anticipated that attaching alkyl chains to five-membered rings, fused to the peripheral sites of the phthalocyanine ring, would result in the adoption of an out-of-plane configuration and thereby discourage cofacial aggregation, to provide an analogy with picket-fence porphyrins. This strategy proved partially successful. Some members of the series of phthalocyanines derived from 2,2-dialkyl-1,3-benzodioxoles, in which the alkyl chains are linked to the phthalocyanine via a cyclic ketal, form spin-coated thin films in which the phthalocyanine cores are perfectly isolated. This behaviour is associated with the formation of a disordered crystal that appears as a mesophase in the thermal profile of these materials. However, the phthalocyanines derived from 2,2-dialkylindanes display a columnar mesophase over a wide temperature range, with some liquid crystalline derivatives at ambient temperature. A single-crystal X-ray diffraction structure of the octahexyl derivative of this series shows how the columnar assembly accommodates the out-of-plane alkyl chains by tilting the macrocyclic plane of the phthalocyanine components with respect to the axis of the column. This study helps to emphasise the importance of both the steric and electronic effects of substituents on the packing behaviour of phthalocyanines in the condensed phase, and especially the role of electron-donating oxygen atoms directly attached to the ring.