Alkyl Side Chains Research Articles

Unlocking the NIR‐II AIEgen for High Brightness through Intramolecular Electrostatic Locking

Fluorescent imaging and biosensing in the near‐infrared‐II (NIR‐II) window holds great promise for non‐invasive, radiation‐free, and rapid‐response clinical diagnosis. However, it’s still challenging to develop bright NIR‐II fluorophores. In this study, we report a new strategy to enhance the brightness of NIR‐II aggregation‐induced emission (AIE) fluorophores through intramolecular electrostatic locking. By introducing sulfur atoms into the side chains of the thiophene bridge in TSEH molecule, the molecular motion of the conjugated backbone can be locked through intramolecular interactions between the sulfur and nitrogen atoms. This leads to enhanced NIR‐II fluorescent emission of TSEH in both solution and aggregation states. Notably, the encapsulated nanoparticles (NPs) of TSEH show enhanced brightness, which is 2.6‐fold higher than TEH NPs with alkyl side chains. The in vivo experiments reveal the feasibility of TSEH NPs in vascular and tumor imaging with a high signal‐to‐background ratio and precise resection for tiny tumors. In addition, polystyrene nanospheres encapsulated with TSEH are utilized for antigen detection in lateral flow assays, showing a signal‐to‐noise ratio 1.9‐fold higher than the TEH counterpart in detecting low‐concentration antigens. This work highlights the potential for developing bright NIR‐II fluorophores through intramolecular electrostatic locking and their potential applications in clinical diagnosis and biomedical research.

Unlocking the NIR-II AIEgen for High Brightness through Intramolecular Electrostatic Locking.

Fluorescent imaging and biosensing in the near-infrared-II (NIR-II) window holds great promise for non-invasive, radiation-free, and rapid-response clinical diagnosis. However, it's still challenging to develop bright NIR-II fluorophores. In this study, we report a new strategy to enhance the brightness of NIR-II aggregation-induced emission (AIE) fluorophores through intramolecular electrostatic locking. By introducing sulfur atoms into the side chains of the thiophene bridge in TSEH molecule, the molecular motion of the conjugated backbone can be locked through intramolecular interactions between the sulfur and nitrogen atoms. This leads to enhanced NIR-II fluorescent emission of TSEH in both solution and aggregation states. Notably, the encapsulated nanoparticles (NPs) of TSEH show enhanced brightness, which is 2.6-fold higher than TEH NPs with alkyl side chains. The in vivo experiments reveal the feasibility of TSEH NPs in vascular and tumor imaging with a high signal-to-background ratio and precise resection for tiny tumors. In addition, polystyrene nanospheres encapsulated with TSEH are utilized for antigen detection in lateral flow assays, showing a signal-to-noise ratio 1.9-fold higher than the TEH counterpart in detecting low-concentration antigens. This work highlights the potential for developing bright NIR-II fluorophores through intramolecular electrostatic locking and their potential applications in clinical diagnosis and biomedical research.

Some Terminally Alkenyl-substituted Porphyrins: Synthesis and Attempts of Heck Reaction Leading to Porphyrin-Azulene Dyads

Abstract:: The synthesis of meso-tetraphenylporphyrin derivatives, double functionalized in one of the phenyl rings (with a nitro group and carbon substituents), is described. 5-(4- Nitroaryl)-10,15,20-triarylporphyrinates react, in the presence of a base (t-BuOK), with carbanions containing a leaving group at the carbanionic center to give products of substitution of hydrogen at ortho-position to the nitro group via vicarious nucleophilic substitution scheme. Their alkylation with allyl bromide or 4-bromobut-1-en (t-BuOK/DMF, at 0-5°C) leads to porphyrins bearing side alkyl chain with a terminal double bond in yields of up to 82%. The double-substituted intermediates are very convenient substrates for Heck cross-coupling reactions. In this study, the synthesis of porphyrin–azulene dyads is reported. In some cases, the formation of highly conjugated systems is observed, with moderate yield. Their structures are interesting from both the porphyrin and azulene point of view.

Compound-specific, intra-molecular, and clumped 13C fractionations in the thermal generation and decomposition of ethane and propane: A DFT and kinetic investigation

The distribution of stable isotopes in organic compounds within geochemical systems reflects the reactions they undergo, which are often kinetically governed and can be elucidated through quantification based on first principles: employing quantum chemical simulations to derive energy barriers and kinetic isotope effects (KIEs), followed by kinetic calculations using these parameters. In this paper, the distribution of 13C in hydrocarbon gases during the thermal generation and decomposition of ethane and propane has been addressed. The work is based on abundant and systematic isotopic data, including the compound- and position-specific 13C compositions, recent improvements in kinetic networks in hydrocarbon generation, and state-of-the-art quantum chemical methods that can process organic geochemical systems involving solid phases. Density Functional Theory computations validate the carbonium path of hydrocarbon generation and the free-radical path of their decomposition under geological conditions. The first step of each path (alkyl sidechain protonation for generation and hydrogen abstraction for decomposition) is the rate-limiting step and determines the 13C fractionations of gaseous hydrocarbons, with the reaction rate constrained by the concentration or accessibility of the active species (hydrated protons and surface free radicals in the two paths, respectively). Alkyl protonation has normal 13C KIEs, but hydrogen abstraction on the surfaces of solid organic matter has inverse ones (substituting 12C by 13C accelerates the reaction). These inverse KIEs explain three isotopic phenomena in gaseous hydrocarbons in their late thermal evolution: 1) the depletion of 13C in ethane and propane accompanied by their decreased fraction in hydrocarbon gases (isotope “rollover”); 2) the reversed 13C sequence with carbon number (δ13Cmethane > δ13Cethane > δ13Cpropane); and 3) the depletion of 13C in the center carbon atoms of residual propane. Isotopic fractionation between gaseous hydrocarbons upon generation is evaluated using the Successive Random Chain-Scission model. The covariation of δ13C in alkanes shows a depletion in CH4 compared with the values expected from the reciprocal of the carbon numbers, indicating that this deviation may be intrinsic instead of mixing with microbial methane. The comparison of intramolecular 13C fractionation of propane between computational and observed data suggests the contribution of isoprenoids at the beginning of the generation, in addition to isotopic homogenization between the center and end carbon atoms through the ring closure of intermediate cations. The 13C–13C clumping exhibits a weak KIE in both the generation and decomposition of ethane; the clumping is essentially stochastically governed. This work demonstrates how first-principle calculations can provide significant insights into the details of geochemical reactions governing the isotopic distributions.

Unlocking the Fluorine-Free Buoy Effect: Surface-Enriched Ruthenium Polypyridine Complexes in Ionic Liquids.

Controlling the local concentration of metal complexes at the surface of ionic liquids (ILs) is a highly sought-after objective due to its pivotal implications in supported ionic liquid phase (SILP) catalysis. Equally important is to avoid per- and polyfluorinated substances due to environmental concerns. Herein, we investigate the surface enrichment of Ru polypyridyl complexes with fluorine-free alkylic side groups of varying lengths and shapes, using the hydrophilic IL [C2C1Im][OAc] as solvent. Additional charged carboxylate groups are included into the polypyridyl ligands to increase the solubility of the complex in the IL. When the ligand system is functionalized with long and hydrophobic alkyl side chains, the complex predominantly localizes at the IL/vacuum interface, as deduced from angle-resolved X-ray photoelectron spectroscopy. Conversely, in the presence of short or more bulky substituents, no surface enrichment is observed. This buoy-like behaviour with fluorine-free side groups is explored for 0.05 %mol to 1 %mol solutions. Intriguingly, surface saturation occurs at approximately 0.5 %mol, which is beneficial to the efficient operation of catalytic systems featuring high surface areas, such as SILP catalysts.

Design and synthesis of SO3H-based ionic liquids for direct catalytic conversion of straw to levulinic acid

The utilization of ionic liquids (ILs) in the conversion of lignocellulose to levulinic acid (LA) is a significant pathway in the field of bio-refinery. In this study, a series of sulfonic-based ILs with elongated alkyl chains were synthesized using density functional theory. These ILs were then utilized for the conversion of straw into LA in a single reaction vessel. The yield of LA was compared between a single solvent (water) and a biphasic system comprising water and methyl isobutyl ketone (MIBK). Among the investigated ILs, [C3SO3HEim]Cl exhibited a higher yield of LA, reaching up to 11.3 wt% in the aqueous phase and 17.8 wt% in the MIBK-water biphasic system. Furthermore, [C3SO3HEim]Cl displayed a high catalytic efficiency (90.4%) and a yield of LA (16.3 wt%) after 5 cycles. These findings suggest that the elongation of alkyl side chains in ILs enhances the solubility of cellulose and increases the yield of LA. The MIBK-water biphasic system promotes the rehydration of hydroxymethylfurfural (HMF) and reduces the residence time of LA in the aqueous phase, thereby optimizing its yield. This innovative approach involving ILs and the MIBK-water biphasic system presents a novel perspective for the production of LA from biomass.

Efficient Functionalization of Organosulfones via Photoredox Catalysis: Direct Incorporation of α-Carbonyl Alkyl Side Chains into α-Allyl-β-Ketosulfones.

A novel and efficient method for functionalizing organosulfones has been established, utilizing a visible-light-driven intermolecular radical cascade cyclization of α-allyl-β-ketosulfones. This process employs fac-Ir(ppy)3 as the photoredox catalyst and α-carbonyl alkyl bromide as the oxidizing agent. Via this approach, the substrates experience intermolecular addition of α-carbonyl alkyl radicals to the alkene bonds, initiating a sequence of C-C bond formations that culminate in the production of organosulfone derivatives. Notably, this technique features gentle reaction conditions and an exceptional compatibility with a wide array of functional groups, making it a versatile and valuable addition to the field of organic synthesis.

Self-Assembly Behavior, Aggregation Structure, and the Charge Carrier Transport Properties of S-Heterocyclic Annulated Perylene Diimide Derivatives.

The construction of high-performance n-type semiconductors is crucial for the advancement of organic electronics. As an attractive n-type semiconductor, molecular systems based on perylene diimide derivatives (PDIs) have been extensively investigated over recent years. Owing to the fascinating aggregated structure and high performance, S-heterocyclic annulated PDIs (SPDIs) are receiving increasing attention. However, the relationship between the structure and the electrical properties of SPDIs has not been deeply revealed, restricting the progress of PDI-based organic electronics. Here, we developed two novel SPDIs with linear and dendronized substituents in the imide position, named linear SPDI and dendronized SPDI, respectively. A series of structural and property characterizations indicated that linear SPDI formed a long-range-ordered crystalline structure based on helical supramolecular columns, while dendronized SPDI, with longer alkyl side chains, formed a 3D-ordered crystalline structure at a low temperature, which transformed into a hexagonal columnar liquid crystal structure at a high temperature. Moreover, no significant charge carrier transport signal was examined for linear SPDI, while dendronized SPDI had a charge carrier mobility of 3.5 × 10-3 cm2 V-1 s-1 and 2.1 × 10-3 cm2 V-1 s-1 in the crystalline and liquid crystalline state, respectively. These findings highlight the importance of the structure-function relationship in PDIs, and also offer useful roadmaps for the design of high-performance organic electronics for down-to-earth applications.

Cross-Reactivity of 24 Cannabinoids and Metabolites in blood using the immunalysis cannabinoids direct enzyme-linked immunosorbent assay kit.

With a wider availability of synthetic and semi-synthetic cannabinoids in the consumer space, there is a growing impact on public health and safety. Forensic toxicology laboratories should keep these compounds in mind as they attempt to remain effective in screening for potential sources of human performance impairment. Enzyme-linked immunosorbent assay (ELISA) is a commonly utilized tool in forensic toxicology, as its efficiency and sensitivity make it useful for rapid and easy screening for a large number of drugs. This screening technique has lower specificity, which allows for broad cross-reactivity among structurally-similar compounds. In this study, the Cannabinoids Direct ELISA kit from Immunalysis was utilized to assess the cross-reactivities of 24 cannabinoids and metabolites in whole blood. The assay was calibrated with 5 ng/mL of 11-nor-9-carboxy-Δ9-tetrahydrocannabinol and the analytes of interest were evaluated at concentrations ranging from 5 to 500 ng/mL. Most parent compounds demonstrated cross-reactivity ≥ 20 ng/mL, with increasing alkyl side chain length relative to Δ9-tetrahydrocannabinol resulting in decreased cross-reactivity. Of the 24 analytes, only the carboxylic acid metabolites, 11-nor-9-carboxy-Δ8-tetrahydrocannabinol, 11-nor-9(R)-carboxy-hexahydrocannabinol, and 11-nor-9(S)-carboxy-hexahydrocannabinol, were cross-reactive at levels ≤ 10 ng/mL. Interestingly, 11-nor-9(R)-carboxy-hexahydrocannabinol demonstrated cross-reactivity at 5 ng/mL, where its stereoisomer 11-nor-9(S)-carboxy-hexahydrocannabinol, did not. As more information emerges about the prevalence of these analytes in blood specimens, it is important to understand and characterize their impact on current testing paradigms.

Nanodomain organization in ionic liquids: Implications of polarization effects in the alkyl side-chain association

The existence of domains at the nanometric scale has been observed in ionic liquids with long alkyl side chains. Experimental evidence and theoretical studies have suggested the existence of nanodomains with polar and non-polar characteristics. This evidence has been related to the capacity of ionic liquids to dissolve species within a broad range of chemical properties. Herein, we present a study of the structural features of the non-polar domain using classical molecular dynamics using a polarizable force field. The results suggest that the tail-to-tail association is stronger when a polarizable force field is used, owing to the better description of the dispersive forces between them. We propose using a polarizable force field in the simulations of ionic liquids based on classical molecular dynamics as the default method. To account for these differences, we compare the non-polarizable force field and its polarizable variant in describing the self-association of long-tailed imidazolium-based ionic liquids. Finally, a nanodomain analysis could rationalize the solute-solvent interactions brought about by ionic liquid since they strongly depend on the hydrogen-bond acidity and basicity, which are expected to operate in the polar domain.

Optimizing Alkyl Side Chains in Difluorobenzene-Rhodanine Small-Molecule Acceptors for Organic Solar Cells.

A series of small molecules, T-2FB-T-ORH, T-2FB-T-BORH, and T-2FB-T-HDRH, were synthesized to have a thiophene-flanked difluorobenzene (T-2FB-T) core and alkyl-substituted rhodanine (RH) end groups for their use as nonfullerene acceptors (NFAs) in organic solar cells (OSCs). Octyl, 2-butyloctyl (BO), and 2-hexyldecyl (HD) alkyl side chains were introduced into RHs to control the material's physical properties based on the length and size of the alkyl chains. The optical properties of the three NFAs were found to be almost the same, irrespective of the alkyl chain length, whereas the molecular crystallinity and material solubility significantly differed depending on the alkyl side chains. Owing to the sufficient solubility of T-2FB-T-HDRH, OSCs based on PTB7-Th and T-2FB-T-HDRH were fabricated. A power conversion efficiency of up to 4.49% was obtained by solvent vapor annealing (SVA). The AFM study revealed that improved charge mobility and a smooth and homogeneous film morphology without excessive aggregation could be obtained in the SVA-treated film.

Physicochemical Properties of 20 Ionic Liquids Prepared by the Carbonate-Based IL (CBILS) Process.

Ionic liquids (ILs) are an emerging materials' class with applications in areas such as energy storage, catalysis, and biomass dissolution and processing. Their physicochemical properties including surface tension, viscosity, density and their interplay between cation and anion chemistry are decisive in these applications. For many commercially available ILs, a full set of physicochemical data is not available. Here, we extend the knowledge base by providing physicochemical properties such as density (20 and 25 °C), refractive index (20 and 25 °C), surface tension (23 °C, including polar and dispersive components), and shear viscosity (ambient atmosphere, shear rate 1-200 s-1), for 20 commercial ILs. A correlation between the crystal volume, dispersive surface tension, and shear viscosity is introduced as a predictive tool, allowing for viscosity estimation. Systematic exploration of cation/anion alkyl side chain lengths reveals the impact on the IL's physicochemical attributes. Increasing the anion's headgroup decreases surface tension up to 35.7% and consequently shear viscosity. We further demonstrate that the dispersive part of the surface tension linearly correlates with the refractive index of the ionic liquid. While we provide additional physicochemical data, the screening and modeling efforts will contribute to better structure property predictions enabling faster progress in design and applications of ILs.

Unraveling the Morphology of [CnC1Im]Cl Ionic Liquids Combining Cluster and Aggregation Analyses.

A characteristic feature of ionic liquids is their nanosegregation, resulting in the formation of polar and nonpolar domains. The influence of increasing the alkyl side chain on the morphology of ionic liquids has been the subject of many studies. Typically, the polar network (charged part of the cation and anion) constitutes a continuous subphase that partially breaks to allow the formation of a nonpolar domain with the increase of the alkyl chain. As the nonpolar network expands, the number of tails per aggregate increases until the ionic liquid percolates. In this work, we demonstrate how the complementary software packages TRAVIS and AGGREGATES can be employed in conjunction to gain insights into the size and morphology of the [CnC1Im]Cl family, with n ∈ {2, 4, 6, 8, 10, 12}. The combination of the two approaches rounds off the picture of the intricate arrangement and structural features of the alkyl chains.

Energy‐Level Alignment and Electronic Structure of Dual‐State Luminogens Thin Films

Organic dual‐state emitters show high quantum yields of luminescence in both solution and the aggregated state. Alkyl side chains are frequently used to engineer solid‐state structures and prominent examples are naphthalimide‐functionalized cyanostilbene derivatives (NICS‐X), where H‐aggregation takes place for ethoxyl substitution (NICS‐E), while methoxyl and butoxyl substitution (NICS‐M and NICS‐B) lead to the quasi‐isolated Q‐type structure. While this takes place for powder samples, vacuum‐sublimed thin films are used, and it is shown by photoluminescence (PL) measurements that H‐aggregation takes place for all three NICS derivatives. In contrast, the energy‐level alignment of NICS‐X films on graphite exhibits disparities as shown by photoelectron spectroscopy: pronounced disorder in NICS‐B films leads to energy‐level bending, while the energy levels of NICS‐M and NICS‐E films remain flat. In such a way, it is demonstrated that side‐chain engineering of luminogens affects the short‐range order (responsible for the PL) and the long‐range order (responsible for the energy‐level alignment) in different ways. Furthermore, the importance of a substrate (thin films vs powder) on the solid‐state aggregation is highlighted.

Crystallization‐Driven Optimization of Morphology and Performance in Near‐Infrared Organic Photodetectors via Alkyl Side Chain Tuning of Narrow Bandgap Non‐Fullerene Acceptors

AbstractNarrow bandgap non‐fullerene acceptors (NBG NFAs) are crucial in advancing near‐infrared organic photodetectors (NIR OPDs). However, the polymorphous behavior of NFAs introduces energetic disorder and charge‐trapping sites in the bulk heterojunction (BHJ) active layers, thereby hindering the NIR performance of OPDs. This study demonstrates the design and optimization of the molecular structures of alkyl side chains in NFAs to morphologically address these electrical limitations and shed light on how side chains affect the crystallization‐driven control of the morphogenesis process in BHJ layers. The structure, linearity, and length of the alkyl side chain molecules are strategically designed and controlled to synthesize a series of NBG NFAs, namely COT‐R (R = EH, BO, Oct, or Dod). The in‐depth quantitative investigations into the morphological and electrical factors reveal that side‐chain optimization effectively enhances various morphological properties, such as the molecular alignment and compatibility between components in the BHJ layer, resulting in the mitigation of energetic disorders and charge traps in the BHJ layers. Therefore, the optimized BHJ system, comprising COT‐Oct blended with PTB7‐Th, achieves a reduced dark current and increased responsivity, contributing to the development of high‐performance NIR OPDs with an impressive specific detectivity of 1.49 × 1012 Jones at 1000 nm under ‐0.5 V.

Spring Lock: Constructing Cluster Emitters with Colorful TADF from Non‐Conjugated Polymaleimide Helical Chains

AbstractNon‐conjugated luminescent polymers have received much attention due to their excellent flexibility, processability, and biocompatibility. However, the single emission color and low solid‐state luminescence efficiency restrict their further development. Herein, by introducing carboxyl‐terminated alkyl chains on the rigid and helical polymaleimide backbone, a series of non‐conjugated luminescent polymers are designed and synthesized. Due to the “spring lock” formed by the synergism of scalable helical main chains and flexible alkyl side chains, these polymers exhibit effective cluster luminescence with thermally activated delayed fluorescence (TADF) property, thereby significantly improving the solid‐state luminescence efficiency with the quantum yield up to 59.6%. The TADF emission wavelengths of the polymer powders can be tuned from 498 to 639 nm through changing reaction solvents, because the conformation of helical chains forming clusters is sensitive to solvent polarity. Interestingly, metal ions can induce the polymers to construct self‐repairing cluster luminescence gels, which show excellent potential applications in ammonia detection and information encryption. This work not only provides an effective design strategy for the colorful cluster luminescence with high‐efficiency TADF, but also further reveals the cluster luminescence mechanism and enlightens the promising applications of cluster luminescent gels.

Theoretical Calculation of Different Side-Chain Lengths [Cnmim]FeCl4 and Factors Influencing Coal Pyrolysis Swelling Modification.

With the increasing requirements for clean and effective utilization, coal swelling pretreatment provides a good theoretical basis for coal molecular structure, application in coal pyrolysis, and liquefaction. Ionic liquids containing magnetic anionic groups were designed, synthesized, and used as solvents to study the effect on swelling pyrolysis performance. Studies have shown magnetism enhancement with the growth of alkyl chains. The growth of the MIL alkyl side chain made the modification effect of coal more obvious, and the swelling degree showed a trend of first increasing and then decreasing with the increase of temperature and time, and at the temperature of 35 °C, the swelling degree is the largest when the modification time is 8 h. Pyrolysis experiments show that magnetic ionic liquid (MIL) pretreatment can significantly reduce the temperature at the maximum weight loss of coal and increase the tar content of pyrolysis, indicating that MIL plays a catalytic cracking role in coal pyrolysis.

Chaetoxylariones A–G: undescribed chromone-derived polyketides from co-culture of Chaetomium virescens and Xylaria grammica enabled via the molecular networking strategy

By co-culturing two endophytic fungi (Chaetomium virescens and Xylaria grammica) collected from the medicinal and edible plant Smilax glabra Roxb. and analyzing them with MolNetEnhancer module on GNPS platform, seven undescribed chromone-derived polyketides (chaetoxylariones A–G), including three pairs of enantiomer ones (2a/2b, 4a/4b and 6a/6b) and four optical pure ones (1, 3, 5 and 7), as well as five known structural analogues (8–12), were obtained. The structures of these new compounds were characterized by NMR spectroscopy, single-crystal X-ray diffraction, 13C NMR calculation and DP4+ probability analyses, as well as the comparison of the experimental electronic circular dichroism (ECD) data. Structurally, compound 1 featured an unprecedented chromone-derived sulfonamide tailored by two isoleucine-derived δ-hydroxy-3-methylpentenoic acids via the acylamide and NO bonds, respectively; compound 2 represented the first example of enantiomeric chromone derivative bearing a unique spiro-[3.3]alkane ring system; compound 3 featured a decane alkyl side chain that formed an undescribed five-membered lactone ring between C-7′ and C-10′; compound 4 contained an unexpected highly oxidized five-membered carbocyclic system featuring rare adjacent keto groups; compound 7 featured a rare methylsulfonyl moiety. In addition, compound 10 showed a significant inhibition towards SW620/AD300 cells with an IC50 value of PTX significantly decreased from 4.09 μM to 120 nM, and a further study uncovered that compound 10 could obviously reverse the MDR of SW620/AD300 cells.

Novel Schiff's base liquid crystalline trifluoromethoxy aniline derivatives of cinnamoyl ester

A novel homologous series of cinnamoyl ester encompassing of twelve homologues liquid crystal samples containing 4′-trifluoromethoxy aniline moiety have been designed and developed to understand their mesophase analysis using polarizing optical microscope, differential scanning calorimetry, spectral analysis and density functional theory approach. The prepared each samples show nematic-smectic A phase with good temperature range of mesophase affected by the variation of side alkyl chains. In addition, present LC samples of cinnamoyl ester trifluro derivatives were tested for their antimicrobial performance and the obtained results reveals a good biological potential for the studied LC homologous series.

Reticular liquid crystal design: Controlling complex self-assembly of p-terphenyl rods by side-chain engineering and chirality

A series of K-shaped bolapolyphiles, consisting of a p-terphenyl core, two polar glycerol end-groups and a swallow-tailed alkyl side-chain were synthesized and investigated. By increasing the side-chain volume an astonishing variety of very different liquid crystalline (LC) phases was observed, ranging from a rectangular (Colrec/c2mm) and a square honeycomb (Colsqu/p4mm) via a highly complex zeolite-like octagon/pentagon honeycomb filled with additional strings of rod-bundles (ColrecZ/c2mm), a new 3D-hexagonal (R3‾c) double network phase, a double and even a single network cubic phase (double gyroid Cub/Ia3‾d and single diamond Cub/Fd3‾m, respectively) to a correlated lamellar phase (LamSm/c2mm). Though these LC structures are highly complex and there is a delicate balance of steric and geometric frustration determining the phase formation, there is only a small effect of permanent molecular chirality in the glycerol groups ((R,R)-configuration) on them, which is attributed to a slightly different packing density of uniformly chiral and racemic glycerols, but not to an effect of induced helicity. Compared to related T-shaped bolapolyphiles with a single linear n-alkyl side-chain, which form exclusively honeycomb phases, the complexity of self-assembly is enhanced for the K-shaped compounds due to a competition between the requirements of space filling, chain stretching and geometric frustration, and affected by the shape of the polar glycerol domains at the junctions.