Counterion effects on the mesomorphic and electrochemical properties of guanidinium salts.

Ionic liquid crystals (ILCs) combine the ion mobility of ionic liquids with the order and self-assembly of thermotropic mesophases. To understand the role of the anion in ILCs, wedge-shaped arylguanidinium salts with tetradecyloxy side chains were chosen as benchmark systems and their liquid crystalline self-assembly in the bulk phase as well as their electrochemical behavior in solution were studied depending on the anion. Differential scanning calorimetry (DSC), polarizing optical microscopy (POM) and X-ray diffraction (WAXS, SAXS) experiments revealed that for spherical anions, the phase width of the hexagonal columnar mesophase increased with the anion size, while for non-spherical anions, the trends were less clear cut. Depending on the anion, the ILCs showed different stability towards electrochemical oxidation and reduction with the most stable being the PF6 based compound. Cyclic voltammetry (CV) and density functional theory (DFT) calculations suggest a possible contribution of the guanidinium cation to the oxidation processes.

Enantioenriched Boron C,N-Chelates via Chirality Transfer.

Molecules stereogenic only at tetrahedral boron atoms show great promise for applications, for example as chiroptical materials, but are scarcely investigated due to their synthetic challenge. Hence, this study reports a two-step synthesis of enantioenriched boron C,N-chelates. First, the diastereoselective complexation of alkyl/aryl borinates with chiral aminoalcohols furnished boron stereogenic heterocycles in up to 86 % yield and d.r. >98 : 2. Treatment of these O,N-complexes with chelate nucleophiles was surmised to transfer the stereoinformation via the ate-complex into the C,N-products. This chirality transfer succeeded by substitution of the O,N-chelates with lithiated phenyl pyridine to give boron stereogenic C,N-chelates in up to 84 % yield and e.r. up to 97 : 3. The chiral aminoalcohol ligands could be recovered after isolation of the C,N-chelates. The chirality transfer tolerated alkyl, alkynyl and (hetero-)aryl moieties at boron and could be further extended by post-modification: transformations such as catalytic hydrogenations or sequential deprotonation/electrophilic trapping were feasible while maintaining the stereochemical integrity of the C,N-chelates. Structural aspects of the boron chelates were studied by variable temperature NMR and X-ray diffraction.

Tailoring liquid crystalline self-assembly and de Vries behavior of azulenes via lateral and core substitution.

The azulene moiety is a highly attractive building block in optoelectronic applications due to its unique properties. For high-performing devices, the molecular orientation is crucial and can be controlled through liquid-crystalline self-assembly. Recent work showed that liquid crystalline derivatives bearing the 2-phenyl-azulene-1-nitrile core formed broad de Vries-type SmA and SmC phases. For exact understanding of the structure-property relationship, a series of 2-(hetero)aryl-azulenes has been synthesized varying the chain linkage, the lateral substituent, and the aromatic ring. Small changes of the molecular structure determined whether the orthogonal SmA phase or the tilted SmC phase is predominant. Implementation of alkyne chains instead of alkoxy chains resulted in the reduction of phase transition temperatures and formation of mesophases at room temperature. Furthermore, de Vries-like behavior was investigated and reduction values between R = 0.35 and 0.74 were measured which supported the hypothesis that in this system de Vries-like behavior is caused by steric repulsion of the lateral substituent. The control of the phase geometry by the molecular structure might be used for improved molecular orientation in optoelectronic materials.

Does thermotropic liquid crystalline self-assembly control biological activity in amphiphilic amino acids? - tyrosine ILCs as a case study.

Amphiphilic amino acids represent promising scaffolds for biologically active soft matter. In order to understand the bulk self-assembly of amphiphilic amino acids into thermotropic liquid crystalline phases and their biological properties a series of tyrosine ionic liquid crystals (ILCs) was synthesized, carrying a benzoate unit with 0-3 alkoxy chains at the tyrosine unit and a cationic guanidinium head group. Investigation of the mesomorphic properties by polarizing optical microscopy (POM), differential scanning calorimetry (DSC) and X-ray diffraction (WAXS, SAXS) revealed smectic A bilayers (SmAd) for ILCs with 4-alkoxy- and 3,4-dialkoxybenzoates, whereas ILCs with 3,4,5-trisalkoxybenzoates showed hexagonal columnar mesophases (Colh), while different counterions had only a minor influence. Dielectric measurements revealed a slightly higher dipole moment of non-mesomorphic tyrosine-benzoates as compared to their mesomorphic counterparts. The absence of lipophilic side chains on the benzoate unit was important for the biological activity. Thus, non-mesomorphic tyrosine benzoates and crown ether benzoates devoid of additional side chains at the benzoate unit displayed the highest cytotoxicities (against L929 mouse fibroblast cell line) and antimicrobial activity (against Escherichia coli ΔTolC and Staphylococcus aureus) and promising selectivity ratio in favour of antimicrobial activity.

Mesogenic Groups Control the Emitter Orientation in Multi-Resonance TADF Emitter Films.

The use of thermally activated delayed fluorescence (TADF) emitters and emitters that show preferential horizontal orientation of their transition dipole moment (TDM) are two emerging strategies to enhance the efficiency of OLEDs. We present the first example of a liquid crystalline multi-resonance TADF (MR-TADF) emitter, DiKTa-LC. The compound possesses a nematic liquid crystalline phase between 80 °C and 110 °C. Importantly, the TDM of the spin-coated film shows preferential horizontal orientation, with an anisotropy factor, a, of 0.28, which is preserved in doped poly(vinylcarbazole) films. Green-emitting (λEL =492 nm) solution-processed OLEDs based on DiKTa-LC showed an EQEmax of 13.6 %. We thus demonstrate for the first time how self-assembly of a liquid crystalline TADF emitter can lead to the so-far elusive control of the orientation of the transition dipole in solution-processed films, which will be of relevance for high-performance solution-processed OLEDs.

Sequential hydrozirconation/Pd-catalyzed cross coupling of acyl chlorides towards conjugated (2E,4E)-dienones.

Dienones are challenging building blocks in natural product synthesis due to their high reactivity and complex synthesis. Based on previous work and own initial results, a new stereospecific sequential hydrozirconation/Pd-catalyzed acylation of enynes with acyl chlorides towards conjugated (2E,4E)-dienones is reported. We investigated a number of substrates with different alkyl and aryl substituents in the one-pot reaction and showed that regardless of the substitution pattern, the reactions lead to the stereoselective formation (≥95% (2E,4E)) of the respective dienones under mild conditions. It was found that enynes with alkyl chains gave higher yields than the corresponding aryl-substituted analogues, whereas the variation of the acyl chlorides did not affect the reaction significantly. The synthetic application is demonstrated by formation of non-natural and natural dienone-containing terpenes such as ß-ionone which was available in 4 steps and 6% overall yield.

Joint Venture of Metal Cluster and Amphiphilic Cationic Minidendron Resulting in Near Infrared Emissive Lamellar Ionic Liquid Crystals.

Inorganic red-NIR emissive materials are particularly relevant in many fields like optoelectronic, bioimaging or solar cells. Benefiting from their emission in devices implies their integration in easy-to-handle materials like liquid crystals, whose long-range ordering and self-healing abilities could be exploited and influence emission. Herein, we present red-NIR emissive hybrid materials obtained with phosphorescent octahedral molybdenum cluster anions electrostatically associated with amphiphilic guanidinium minidendrons. Polarized optical microscopy and X-ray analysis show that while the minidendron chloride salts self-organize into columnar phases, their association with the dianionic metal cluster leads to layered phases. Steady-state and time-resolved emission investigations demonstrate the influence of the minidendron alkyl chain length on the phosphorescence of the metal cluster core.

Chasing Self-Assembly of Thioether-Substituted Flavylium Salts in Solution and Bulk State.

Two series of flavylium triflates carrying alkoxy side chains in the A-ring (benzo unit of chromylium salt) and thioethers in the B ring (phenyl unit) (On -Fla-Sm ) as well as thioethers at both A and B ring (Sn -Fla-Sm ) were synthesized in order to understand the effect of thioether functionalization on their self-assembly and electronic properties. Concentration-dependent and diffusion ordered (DOSY) NMR experiments of O1 -iV-Fla-S3 indicate the formation of columnar H-aggregates in solution with antiparallel intracolumnar stacking of the AC unit (chromylium) of the flavylium triflate, in agreement with the solid state structure of O1 -V-Fla-S1 . Thioether substitution on the B ring changes the linear optical properties in solution, whereas it has no effect on the A ring. According to differential scanning calorimetry, polarizing optical microscopy and X-ray diffraction bulk self-assembly of these ionic liquid crystals (ILCs) depends on the total number of side chains, yielding SmA and LamCol phases for ILCs with 2-3 chains and Colro , Colh phases for ILCs with 3-6 chains. Thus, we demonstrated that thioethers are a useful design tool for ILCs with tailored properties.

N-Alkylimidazolium carboxylates as a new type of catanionic surface active ionic liquid: synthesis, thermotropic behavior and micellization in water.

Aiming at a new type of salt-free CASAIL (Catanionic Surface Active IL) for electrochemical applications or emulsifiers, dispersants, and foaming or antifoaming agents, we combined mesogenic anions (carboxylate) and cations (imidazolium) of similar shape and size to synthesize a series of congruent ion pairs of 1-alkyl-3-methylimidazolium alkylcarboxylates [Cnmim][Cm-1COO] (n = 10-16, m = 10-16). With particular focus on alkyl chain length varieties in both, imidazolium cations and carboxylate anions (n/m), the self-assembly in the bulk phase and in solution was investigated by differential scanning calorimetry (DSC), polarized optical microscopy (POM), X-ray diffraction (XRD) experiments and surface tension measurements. Our results revealed that the presence of long alkyl chains on both the cation n and anion m leads to improved thermal stability of the bulk material while maintaining broad lamellar (SmA) mesophases. In water, we observed a strong and linear decrease of log(cmc) for increasing both the carboxylate anion and imidazolium cation chain length due to the increasing hydrophobic effect. Surprisingly, for both thermotropic behavior and micellization, the chain length of the carboxylate anion had a stronger impact than the chain length of the imidazolium cation, indicating its greater surface activity and tendency to form micelles.

Modulating chitin synthesis in marine algae with iminosugars obtained by SmI2 and FeCl3-mediated diastereoselective carbonyl ene reaction.

Strategies for synthesizing polyhydroxylated piperidines such as iminosugars have received broad attention. These substances are known to interact with carbohydrate related enzymes, glycosidases and glycosyltransferases, to which also the large enzyme families of chitin synthases and cellulose synthases belong. Many chemical and biological aspects of chitin synthases remain unexplored due to the fact that modulating substances are hardly available or expensive. Starting from enantiopure D- and L-amino acids, a series of iminosugars was prepared by a Lewis acid-catalyzed cyclization of amino acid-derived unsaturated aldehydes as key step. Therefore, different Lewis acids were tested. For samarium diiodide we observed a superior stereoselectivity in comparison to iron(III) chloride and methylaluminium dichloride. To increase water solubility for testing and measurement of enzyme activity, the cyclization products were further functionalized. We established a novel biological chitin synthesis test system which allows quantitative investigation of chitin synthesis in the chitin fiber producing diatom algae Thalassiosira in vivo under the light microscope. None of the compounds displayed cytotoxicity, but two of the four iminosugars increased the length of the chitin fibers produced. This is a strong indicator that these compounds mimic carbohydrates responsible for restarting chitin polymerization.

Liquid crystalline self-assembly of azulene-thiophene hybrids and their applications as OFET materials.

Orientational control within thin films is crucial for the preparation of organic field effect transistors (OFETs). The highly ordered liquid crystalline smectic E phase (SmE) is known as a powerful template for solution processed thin films. Here, we describe the synthesis and characterization of three novel azulene-thiophene hybrid materials. Liquid crystalline characterization showed the presence of wide SmE phases. Thin films were prepared by spin-coating at mesophase temperature. Due to the self-aligning properties of the SmE phase uniformly flat films with good molecular alignment were manufactured. Top contact bottom gate OFETs showed mobilities up to (3.3 ± 0.5) × 10-3 cm2 V-1 s-1.

Merging liquid crystalline self-assembly and linear optical properties of merocyanines via tailored donor units.

Aiming at merocyanine dyes with good linear optical and self-assembly properties, a series of rigid mono-, bi- and tricyclic merocyanines with O- and N-donor units as well as keto or malodinitrile acceptor units was prepared by a convergent approach. With particular focus on tailoring the donor unit, a selection of appropriate derivatives was investigated with respect to their dye properties in solution and in the bulk (UV/Vis, fluorescence, temperature-dependent fluorescence, lifetime). Determination of fluorescence quantum yields revealed the importance of the donor unit and the chromophore size. Larger chromophores and N-donors were beneficial for strong emission in solution, whereas small chromophores and O-donors favored emission in the solid state. To rationalize the different optical properties depending on their donor unit, density functional theory (DFT) calculations were performed. Liquid crystalline derivatives were additionally studied by optical polarization microscopy, differential scanning calorimetry, and X-ray diffraction experiments. For merocyanines with O-donor, fluorinated side chains were mandatory to get stable enantiotropic SmA phases regardless of chromophore size, side chain lengths or acceptor unit. Increased mesophase widths (up to 134 K) were observed upon increasing the chromophore lengths, chain lengths (up to C12) and F/C ratio in the side chain. On the other hand, merocyanines with N-donor and keto acceptor showed enantiotropic SmA phases in the presence of simple alkoxy side chains. The tricyclic merocyanine with N-donor shows an additional SmE phase at lower temperatures. The results revealed the importance of the donor unit to balance optical and mesomorphic properties in merocynanines.

Interplay of Polarity and Confinement in Asymmetric Catalysis with Chiral Rh Diene Complexes in Microemulsions.

Microemulsions provide a unique opportunity to tailor the polarity and liquid confinement in asymmetric catalysis via nanoscale polar and nonpolar domains separated by a surfactant film. For chiral diene Rh complexes, the influence of counterion and surfactant film on the catalytic activity and enantioselectivity remained elusive. To explore this issue chiral norbornadiene Rh(X) complexes (X=OTf, OTs, OAc, PO2 F2 ) were synthesized and characterized by X-ray crystallography and theoretical calculations. These complexes were used in Rh-catalyzed 1,2-additions of phenylboroxine to N-tosylimine in microemulsions stabilized either exclusively by n-octyl-ß-D-glucopyranoside (C8 G1 ) or a C8 G1 -film doped with anionic or cationic surfactants (AOT, SDS and DTAB). The Rh(OAc) complex showed the largest dependence on the composition of the microemulsion, yielding up to 59 % (90 %ee) for the surfactant film doped with 5 wt% of AOT as compared to 52 % (58 %ee) for neat C8 G1 at constant surfactant concentration. Larger domains, determined by SAXS analysis, enabled further increase in yield and selectivity while the reaction rate almost remained constant according to kinetic studies.

Synthesis of Highly Functionalized Hydrindanes via Sequential Organocatalytic Michael/Mukaiyama Aldol Addition and Telescoped Hydrozirconation/Cross-Coupling as Key Steps: En Route to the AB System of Clifednamides.

The AB ring systems of the clifednamide family, polycyclic tetramate macrolactames (PoTeMs), were prepared by a new, convergent approach employing an intramolecular Diels-Alder (IMDA) reaction. Key steps comprise an organocatalytic Michael addition (>90% enantiomeric excess (ee)), a Mukaiyama aldol reaction for the convergent installation of a diene moiety, and a telescoped hydrozirconation/cross-coupling grafting an enone. The following IMDA furnished a highly functionalized hydrindane (diastereomeric ratio (dr) = 91:1) with the same configuration as the clifednamide scaffold. Advantages of this route are only one required protecting group, 13% overall yield over 9 steps (reduced from previously 17 steps/1.3% overall), and the potential access to the key intermediates in the clifednamide biosynthesis.

Self-Assembly of Aminocyclopropenium Salts: En†Route to Deltic Ionic Liquid Crystals.

Aminocyclopropenium ions have raised much attention as organocatalysts and redox active polymers. However, the self-assembly of amphiphilic aminocyclopropenium ions remains challenging. The first deltic ionic liquid crystals based on aminocyclopropenium ions have been developed. Differential scanning calorimetry, polarizing optical microscopy and X-ray diffraction provided insight into the unique self-assembly and nanosegregation of these liquid crystals. While the combination of small headgroups with linear p-alkoxyphenyl units led to bilayer-type smectic mesophases, wedge-shaped units resulted in columnar mesophases. Upon increasing the size and polyphilicity of the aminocyclopropenium headgroup, a lamellar phase was formed.

Intramolecular Borylation via Sequential B-Mes Bond Cleavage for the Divergent Synthesis of B,N,B-Doped Benzo[4]helicenes.

New symmetric and unsymmetric B,N,B-doped benzo[4]helicenes 3-6 a/b have been achieved in good yields, using a three-step process, starting from N(tolyl)3 in a highly divergent manner (7 examples). A borinic acid functionalized 1,4-B,N-anthracene 1 was found to display unprecedented reactivity, acting as a convenient and highly effective precursor for selective formation of bromo-substituted B,N,B-benzo[4]helicenes 2 a/2 b via intramolecular borylation and sequential B-Mes bond cleavage in the presence of BBr3 . Subsequent reaction of 2 a/2 b with Ar-Li provided a highly effective toolbox for the preparation of symmetrically/unsymmetrically functionalized B,N,B-helicenes. Their high photoluminescence quantum yields along with the small ΔEST suggest their potential as thermally activated delayed fluorescence (TADF) emitters for organic light-emitting diodes (OLEDs).

Flavylium Salts: A Blooming Core for Bioinspired Ionic Liquid Crystals.

Thermotropic ionic liquid crystals based on the flavylium scaffold have been synthesized and studied for their structure-properties relationship for the first time. The mesogens were probed by differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and X-ray diffraction (XRD). Low numbers of alkoxy side chains resulted in smectic (SmA) and lamello-columnar (LamCol ) phases, whereas higher substituted flavylium salts showed Colro as well as ordered and disordered columnar (Colho , Colhd ) mesophases. Mesophase width ranged from 13 K to 220 K, giving access to room temperature liquid crystals. The optical properties of the synthesized compounds were probed towards absorption and emission properties. Strong absorption with maxima between 444 and 507 nm was observed, and some chromophores were highly emissive with quantum yields up to 99 %. Ultimately, mesogenic and dye properties were examined by temperature-dependent emissive experiments in the solid state.

Asymmetric Catalysis in Liquid Confinement: Probing the Performance of Novel Chiral Rhodium-Diene Complexes in Microemulsions and Conventional Solvents.

The role of liquid confinement on the asymmetric Rh catalysis was studied using the 1,2-addition of phenylboroxine (2) to N-tosylimine 1 in the presence of [RhCl(C2 H4 )2 ]2 and chiral diene ligands as benchmark reaction. To get access to Rh complexes of different polarity, enantiomerically pure C2 -symmetric p-substituted 3,6-diphenylbicyclo[3.3.0]octadienes 4 and diastereomerically enriched unsymmetric norbornadienes 5 and 6 carrying either the Evans or the SuperQuat auxiliary were synthesized. A microemulsion containing the equal amounts of H2 O/KOH and toluene/reactants was formulated using the hydrophilic sugar surfactant n-octyl ß-d-glucopyranoside (C8 G1 ) to mediate the miscibility between the nonpolar reactants and KOH, needed to activate the Rh-diene complex. Prominent features of this organized reaction medium are its temperature insensitivity as well as the presence of water and toluene-rich compartments with a domain size of 55 Šconfirmed by small-angle X-ray scattering (SAXS). Although bicyclooctadiene ligands 4 a,b,e performed equally well under homogeneous and microemulsion conditions, ligands 4 c,d gave a different chemoselectivity. For norbornadienes 5, 6, however, microemulsions markedly improved conversion and enantioselectivity as well as reaction rate, as was confirmed by kinetic studies using ligand 5 b.

Self-Assembly and Fluorescence of Tetracationic Liquid Crystalline Tetraphenylethene.

A series of tetraguanidinium tetraphenylethene (TPE) arylsulfonates with different chain lengths was prepared via ionic self-assembly of tetraguanidinium TPE chloride and the respective methyl arylsulfonates. Liquid crystalline properties were studied by differential scanning calorimetry, polarizing optical microscopy and X-ray diffraction. Tetraguanidinium TPE arylsulfonates with chain lengths of C8 -C12 displayed hexagonal columnar mesophases over a broad temperature range, while derivatives with longer chains showed oblique columnar phases. In solution all compounds displayed aggregation-induced emission behaviour. Temperature-dependent luminescence spectra of the bulk phase of the tetraguanidinium TPE arylsulfonate with C14 side chains revealed a strong luminescence both in the solid state and the oblique columnar mesophase. The emission behaviour was rationalized by a unique combination of restriction of intramolecular rotation of the TPE core, Coulomb interaction between the guanidinium cations and π-π interactions of the anionic arylsulfonate moieties.

Samarium Iodide-Promoted Asymmetric Reformatsky Reaction of 3-(2-Haloacyl)-2-oxazolidinones with Enals.

3-(2-Haloacyl)-2-oxazolidinones were shown to react with enals in an asymmetric SmI2-promoted Reformatsky reaction to give stereochemically well-defined 3-hydroxy-4-alkenyl- and 3-hydroxy-2-methyl-4-alkenyl imides. Chirality transfer of the Evans (S)-oxazolidinone unit via a Zimmerman-Traxler-like transition state resulted in Reformatsky products with a relative syn-configuration. The absolute configuration of compounds obtained is opposite to the corresponding products obtained via aldol addition of boron enolates to enals using the same Evans oxazolidinones.