Hydrogen Bonding as a Supramolecular Tool for Robust OFET Devices

In the present study, we demonstrated the effect of hydrogen bonding in the semiconducting behaviour of a small molecule used in organic field-effect transistors (OFETs). For this study, the highly soluble dumbbell-shaped molecule, Boc-TATDPP based on a Boc-protected thiophene-diketopyrrolopyrrole (DPP) and triazatruxene (TAT) moieties was used. The two Boc groups of the molecule were removed by annealing at 200 °C, which created a strong hydrogen-bonded network of NH-TATDPP supported by additional π–π stacking. These were characterised by thermogravimetric analysis (TGA), UV/Vis and IR spectroscopy, XRD and high-resolution (HR)-TEM measurements. FETs were fabricated with the semiconducting channel made of Boc-TATDPP and NH-TATDPP separately. It is worth mentioning that the Boc-TATDPP film can be cast from solution and then annealed to get the other systems with NH-TATDPP. More importantly, NH-TATDPP showed significantly higher hole mobilities compared to Boc-TATDPP. Interestingly, the high hole mobility in the case of NH-TATDPP was unaffected upon blending with [6,6]-phenyl-C71-butyric acid methyl ester (PC₇₁BM). Thus, this robust hydrogen-bonded supramolecular network is likely to be useful in designing efficient and stable organic optoelectronic devices.     

Autoamplification of Molecular Chirality through the Induction of Supramolecular Chirality

The novel concept for the autoamplification of molecular chirality, wherein the amplification proceeds through the induction of supramolecular chirality, is presented. A solution of prochiral, ring‐open diarylethenes is doped with a small amount of their chiral, ring‐closed counterpart. The molecules co‐assemble into helical fibers through hydrogen bonding and the handedness of the fibers is biased by the chiral, ring‐closed diarylethene. Photochemical ring closure of the open diarylethene yields the ring‐closed product, which is enriched in the template enantiomer.     

Supramolecular control of charge-transfer dynamics on dye-sensitized nanocrystalline TiO2 films

A [Ru(dcbpy)(2)(NCS)(2)] dye has been chemically modified by the addition of a secondary electron donor moiety, N,N-(di-p-anisylamino)phenoxymethyl. Optical excitation of the modified dye adsorbed to nanocrystalline TiO(2) films shows a remarkably long-lived charge-separated state, with a decay half time of 0.7 s. Semiempirical calculations confirm that the HOMO of the modified dye molecule is localised on the electron donor group. The retardation of the recombination dynamics relative to the unmodified control dye is caused by the increase in the spatial separation of the HOMO orbital from the TiO(2) surface. The magnitude of the retardation is shown to be in agreement with that predicted from the non-adiabatic electron-tunnelling theory.     

Chiral supramolecular assemblies of a squaraine dye in solution and thin films: concentration-, temperature-, and solvent-induced chirality inversion

We prepared novel cholesterol-appended squaraine dye 1 and model squaraine dye 2 and investigated their aggregation behavior in solution and thin films using photophysical, chiroptical, and microscopic techniques. Investigations on the dependence of aggregation on solvent composition (good/poor, CHCl3/CH3CN) demonstrated that squaraine dye 1 forms two novel H-type chiral supramolecular assemblies with opposite chirality at different good/poor solvent compositions. Model compound 2 formed J-type achiral assemblies under similar conditions. The supramolecular assembly of 1 observed at lower fractions of the poor solvent could be assigned to the thermodynamically stable form, while a kinetically controlled assembly is formed at higher fractions of the poor solvent. This assignment is evidenced by temperature- and concentration-dependent experiments. With increasing temperature, the chirality of the kinetically controlled aggregate was lost and, on cooling, the aggregate with the opposite chirality was formed. On further heating and cooling the aggregates thus formed resulted in no significant changes in chirality, that is they are thermodynamically stable. Similarly, at lower concentrations, the thermodynamically stable form exists, but at higher concentration aggregation was found to proceed with kinetic control. Based on these observations it can be assumed that formation of the kinetically controlled assembly might be largely dependent on the presence of the nonpolar cholesterol moiety as well as the amount of poor solvent present. However, under solvent-free conditions, structurally different aggregates were observed when drop cast from solutions containing monomer, whereas a left-handed CD signal corresponding to the thermodynamically controlled assemblies was observed from pre-aggregated solutions.     

Characterization of Supramolecular Hidden Chirality of Hydrogen‐Bonded Networks by Advanced Graph Set Analysis

Supramolecular hidden chirality of hydrogen‐bonded (HB) networks of primary ammonium carboxylates was exposed by advanced graph set analysis from a symmetric viewpoint in topology. The ring‐type HB (R‐HB) networks are topologically regarded as faces, and therefore exhibit prochirality and positional isomerism due to substituents attached on the faces. To describe the symmetric properties of the faces, additional symbols, Re (right‐handed or clockwise), Si (left‐handed or anticlockwise), and m (mirror), were proposed. According to the symbols, various kinds of faces were classified based on the symmetry. This symmetry consideration of the faces enables us to precisely evaluate supramolecular chirality, especially its handedness, of 0D‐cubic, 1D‐ladder and 2D‐sheet HB networks that are composed of the faces. The 1D‐ladder and 2D‐sheet HB networks generate chirality by accumulating the chiral faces in 1D and 2D manners, respectively, whereas 0D‐cubic HB networks generate chirality based on combinations of eight kinds of faces, similar to the chirality of dice.     

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.     

Micro‐ and Nanometer‐Scale Porous,Fibrous, and Sheet Architectures Constructed by Supramolecular Assemblies of Dipyrrolyldiketones

X‐ray analysis of some 1,3‐dipyrrolyl‐1,3‐propanediones synthesized from pyrroles and malonyl chloride derivatives revealed 1D supramolecular networks formed by N? H???O?C interactions in the solid state. Micro‐ and nanometer‐scale morphologies of porous, fibrous, and sheet structures were fabricated by hydrogen‐bonding interactions and determined by fine‐tuning the substituents and the solvents used. Of the unique polymorphs, ordered 2D lamellar sheet structures of the derivatives with long alkyl chains (C₁₆H₃₃, C₁₄H₂₉, and so on) were constructed by van der Waals hydrophobic effects between aliphatic chains as well as hydrogen bonding.     

Supramolecular Architectures from Bent‐Core Dendritic Molecules

Control of the self‐assembly of small molecules to generate architectures with diverse shapes and dimensions is a challenging research field. We report unprecedented results on the ability of ionic, bent dendritic molecules to aggregate in water. A range of analytical techniques (TEM, SEM, SAED, and XRD) provide evidence of the formation of rods, spheres, fibers, helical ribbons, or tubules from achiral molecules. The compact packing of the bent‐core structures, which promotes the bent‐core mesophases, also occurs in the presence of a poor solvent to provide products ranging from single objects to supramolecular gels. The subtle balance of molecule/solvent interactions and appropriate molecular designs also allows the transfer of molecular conformational chirality to morphological chirality in the overall superstructure. Functional motifs and controlled morphologies can be combined, thereby opening up new prospects for the generation of nanostructured materials through a bottom‐up strategy.     

Self‐Healing Materials from V‐ and H‐Shaped Supramolecular Architectures

Integrating self‐healing capability into supramolecular architectures is an interesting strategy, and can considerably enhance the performance and broaden the scope of applications for this important class of polymers. Herein we report the rational design of novel V‐shaped barbiturate (Ba) functionalized soft–hard–soft triblock copolymers with a reversible supramolecular healing motif (Ba) in the central part of the hard block, which undergoes autonomic repair at 30 °C. The designed synthesis also offers a suitable macromolecular building block to further self‐assemble with heterocomplementary α,ω‐Hamilton wedge (HW) functionalized polyisoprene (PI; HW‐PI‐HW), resulting in an H‐shaped supramolecular architecture with efficient self‐healing capabilities that can recover up to around 95 % of the original mechanical performance at 30 °C within 24 h.     

基于氢键作用结合的超分子聚合物

非共价键结合的超分子聚合物由于其特殊的结构及性能引起了广泛的关注。本文在介绍超分子化学、氢键及超分子聚合物的基础上,主要综述了以氢键为结合力的多重氢键作用、羧基（D）与吡啶基（A）作用以及氢键与其它非共价键协同作用形成的超分子聚合物体系,并对超分子聚合物的研究现状及前景进行了评述。     

Molecular Encapsulation of Fluorescent Dyes Affords Efficient Narrow‐band Dye Laser Operation in Water

A water‐based narrow‐band high‐efficiency dye laser was designed by means of a supramolecular host–guest chemical approach. The lasing characteristics of rhodamine B and sulforhodamine B (Kiton Red S) dyes in aqueous solution with the macrocyclic host cucurbit[7]uril (CB7) as additive were investigated in a narrow‐band dye laser setup. Significant improvements in both photostability and thermo‐optical properties of the aqueous CB7‐complexed dye systems were observed as compared to the uncomplexed dyes in ethanol solution. The tuning curves for the new dye–CB7–water systems were constructed by measuring the laser output at different wavelengths, which showed similar peak efficiencies and red‐shifted gains compared to the ethanolic solutions of the dyes, while dye laser operation revealed comparable pump threshold energies and slope efficiencies. The combined results render the dye–CB7–water system an attractive active medium for high‐repetition rate dye laser operation.