4-pentynoic Acid Research Articles

Synthesis of a BC-Dihydrodipyrrin Building Block of Bacteriochlorophyll a.

A strategy for the synthesis of bacteriochlorophyll a relies on joining AD and BC halves that contain the requisite stereochemical configurations of the target macrocycle. The BC half (1) is a dihydrodipyrrin bearing a dimethoxymethyl group at the 1-position, a β-ketoester at the 8-position, and (R)-2-methyl and (R)-3-ethyl substituents in the pyrroline ring. An established route to AD-dihydrodipyrrins (Pd-mediated coupling of a 2-halopyrrole with a chiral 4-pentynoic acid followed by Petasis methenylation, acidic hydrolysis, Paal-Knorr ring closure, and Riley oxidation) proved to be unviable for BC-dihydrodipyrrins given the presence of the β-ketoester unit. A route presented here entails Pd-mediated coupling of a 2-halopyrrole (2) with (3R,4R)-4-ethyl-1,1-dimethoxy-3-methylhex-5-yn-2-one (3), anti-Markovnikov hydration of the alkyne to give the 1,4-diketone, and Paal-Knorr ring closure. Compound 3 was prepared by Schreiber-modified Nicholas reaction beginning with (S)-4-isopropyl-3-propionyloxazolidin-2-one and the hexacarbonyldicobalt complex of (±) 3-methoxy-1-(trimethylsilyl)pentyne followed by transformation of the aldehyde derived therefrom to the 1,1-dimethoxymethylcarbonyl motif. The absolute stereochemical configuration of the Schreiber-Nicholas alkylation product was confirmed by single-crystal X-ray diffraction, whereas the BC half (1) by 1H NMR spectroscopy showed a J value of 2.9 Hz consistent with the trans-configuration. Taken together, the route provides a key chiral building block for the synthesis of photosynthetic tetrapyrroles and analogues.

Supramolecular Control of the Oxidative Addition as a Way To Improve the Catalytic Efficiency of Pincer-Rhodium (I) Complexes.

1 H NMR studies using a cationic complex with a pyridine-di-imidazolylidene pincer ligand of formula [Rh(CNC)(CO)]+ revealed that this compound showed high binding affinity with coronene in CH2 Cl2 . The interaction between coronene and the planar RhI complex is established by means of π-stacking interactions. This interaction has a strong impact on the electron-donating strength of the pincer CNC ligand, which is increased significantly, as demonstrated by the shifting of the ν(CO) stretching bands to lower frequencies. The addition of coronene increases the reaction rate of the nucleophilic attack of methyl iodide on the rhodium (I) pincer complex, and also has a positive effect on the performance of the complex as a catalyst in the cycloisomerization of 4-pentynoic acid. These findings highlight the importance of supramolecular interactions for tuning the reactivity and catalytic activity of square-planar metal complexes.

Well-Defined Heparin Mimetics Can Inhibit Binding of the Trimeric Spike of SARS-CoV-2 in a Length-Dependent Manner.

The emergence of new SARS-CoV-2 variants and the dangers of long-covid necessitate the development of broad-acting therapeutics that can reduce viral burden. SARS-CoV-2 employs heparan sulfate (HS) as an initial cellular attachment factor, and therefore, there is interest in developing heparin as a therapeutic for SARS-CoV-2. Its use is, however, complicated by structural heterogeneity and the risk of causing bleeding and thrombocytopenia. Here, we describe the preparation of well-defined heparin mimetics by a controlled head-to-tail assembly of HS oligosaccharides having an alkyne or azide moiety by copper-catalyzed azide-alkyne cycloaddition (CuAAC). Alkyne- and azide-containing sulfated oligosaccharides were prepared from a common precursor by modifying an anomeric linker with 4-pentynoic acid and by enzymatic extension with an N-acetyl-glucosamine having an azide moiety at C-6 (GlcNAc6N3), respectively, followed by CuAAC. The process of enzymatic extension with GlcNAc6N3 followed by CuAAC with the desired alkyne-containing oligosaccharides could be repeated to give compounds composed of 20 and 27 monosaccharides, respectively. The heparin mimetics could inhibit the binding of the SARS-CoV-2 spike or RBD to immobilized heparin or to Vero E6 cells. The inhibitory potency increased with increasing chain length, and a compound composed of four sulfated hexasaccharides linked by triazoles had a similar potency as unfractionated heparin. Sequence analysis and HS microarray binding studies with a wide range of RBDs of variants of concern indicate that they have maintained HS-binding capabilities and selectivities. The heparin mimetics exhibit no or reduced binding to antithrombin-III and platelet factor 4, respectively, which are associated with side effects.

Endohedrally Functionalized Metal–Organic Cage-Cross-Linked Polymer Gels as Modular Heterogeneous Catalysts

The immobilization of homogeneous catalysts onto supports to improve recyclability while maintaining catalytic efficiency is often a trial-and-error process limited by poor control of the local catalyst environment and few strategies to append catalysts to support materials. Here, we introduce a modular heterogenous catalysis platform that addresses these challenges. Our approach leverages the well-defined interiors of self-assembled Pd12L24 metal-organic cages/polyhedra (MOCs): simple mixing of a catalyst-ligand of choice with a polymeric ligand, spacer ligands, and a Pd salt induces self-assembly of Pd12L24-cross-linked polymer gels featuring endohedrally catalyst-functionalized junctions. Semi-empirical calculations show that catalyst incorporation into the MOC junctions of these materials has minimal affect on the MOC geometry, giving rise to well-defined nanoconfined catalyst domains as confirmed experimentally using several techniques. Given the unique network topology of these freestanding gels, they are mechanically robust regardless of their endohedral catalyst composition, allowing them to be physically manipulated and transferred from one reaction to another to achieve multiple rounds of catalysis. Moreover, by decoupling the catalyst environment (interior of MOC junctions) from the physical properties of the support (the polymer matrix), this strategy enables catalysis in environments where homogeneous catalyst analogues are not viable, as demonstrated for the Au(I)-catalyzed cyclization of 4-pentynoic acid in aqueous media.

Optimized Methods for the Production and Bioconjugation of Site-Specific, Alkyne-Modified Glucagon-like Peptide-1 (GLP-1) Analogs to Azide-Modified Delivery Platforms Using Copper-Catalyzed Alkyne-Azide Cycloaddition.

This study aimed to develop and optimize chemistries to produce alkyne-modified glucagon-like peptide-1(7-36)-amide (GLP-1(7-36)-NH2) libraries, which could be rapidly and efficiently conjugated to other components and screened to identify compounds with the best drug delivery properties, as potential treatments for type 2 diabetes or obesity. For this purpose, the Lys26 (K26) side-chain, and the amino (N)- and carboxy (C)-termini of a dipeptidyl peptidase 4 (DPPIV)-resistant GLP-1 sequence (GLP-1(7-36;A8G)-NH2), were modified with an alkyne (4-pentynoic acid or propiolic acid). These analogs were characterized with respect to human GLP-1 receptor (hGLP-1R) agonist activity, effects on cell viability and human serum stability, revealing that these modifications maintained low (N-terminal; EC50 1.5 × 10-9 M) to subnanomolar (C-terminal and K26, ∼4 × 10-10 M) agonist activity toward hGLP-1, had no effect on cell viability, and for the N-terminal and K26 modifications, increased human serum proteolytic stability (t1/2 > 24 h). Copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction conditions were investigated using the C-terminal modified GLP-1 analog and an azide-modified model lipid peptide, with respect to the effects of altering the azide/alkyne ratio, cosolvents, temperature, reducing agents, Cu(I)-stabilizing ligand, copper source, and the concentrations of reagents/reactants, in order to identify general conditions that provide fast reactions and high yields. A 1:2 azide-alkyne (lipid:GLP-1 peptide) and 4:1 sodium ascorbate/copper sulfate molar ratio in 65% v/v DMSO-water at room temperature, in the absence of Cu(I)-stabilizing ligands (THPTA or l-histidine) and buffers (phosphate, pH 7), provided the best yields. This work reports a library of characterized GLP-1 analogs and chemistries for their attachment to other species, providing useful tools to improve GLP-1 delivery and pharmacology (e.g., through conjugation to other species that lower blood glucose, increase the duration of action, or enable delivery via a nonparenteral route).

SiO2-BiCl3 as Heterogeneous Catalyzed Synthesis of 6-Methyl-2-aryl-4,5-dihydropyridazin-3(2H)-one Derivatives

A mild and highly efficient stereoselective reaction using silica supported bismuth(III) chloride (SiO2-BiCl3) has been successfully employed in the synthesis of 6-methyl-2-aryl-4, 5-dihydropyridazin-3(2H)-one derivatives (3a-o) with a variety of phenyl hydrazines (1a-o) bearing either electron withdrawing or donating functional groups and 4-pentynoic acid (2). The catalyzed reaction proceeded smoothly under room temperature in THF to give the corresponding 3a-o derivatives in good to excellent yields. The 3a-o derivatives have been characterized by IR, 1H NMR, 13C NMR, mass and elemental analysis. The use of this approach allowed us to rapidly screen a selection of conditions and quickly confirm the viability of preparing the target 3a-o derivatives in short reaction times.

Click regulation of cyclodextrin primary face for the preparation of novel chiral stationary phases.

In this study, a series of novel CD chiral stationary phases were fabricated by immobilization of mono-6A -deoxy-N3 -cyclodextrin onto silica surfaces followed by click regulation of CD primary face with 4-pentynoic acid (acidic moiety), 2-propynylamine (alkaline moiety) and L-propargylglycine (chiral amino acid moiety), respectively. Enantioseparations of various kinds of racemates including dansyl-amino acids, chiral lactides and diketones were conducted in reversed phase modes on these chiral stationary phases, where nearly forty diketones and chiral lactides were firstly separated on cyclodextrin stationary phases. 4-Pentynoic acid moiety can make the retention ability decline while amine moiety significantly enhanced the retention ability of the stationary phases. For most of the studied analytes, the chiral amino acid moiety had the most positive effects on both the retention time and the resolution. The inclusion complexation between chiral analytes and cyclodextrins were also investigated by fluorescence method.

Palladium pincer complexes featuring an unsymmetrical SCN indene-based ligand with a hemilabile pyridine sidearm.

A new unsymmetrical indene-based pro-ligand featuring thiophosphinoyle and methylpyridine sidearms 2 was prepared. Coordination and cyclometalation in the presence of [PdCl2(PhCN)2] and PS-DIEA afforded three well-defined 2-indenyl SCN pincer complexes 3a-c. The lability of the pyridine moiety has been evidenced upon treatment with triphenylphosphine and 2,6-dimethylphenylisocyanide. In addition, reversible C-Pd bond cleavage has been demonstrated under Brønsted acid/base conditions. The indenediide SCN pincer complex 4 was prepared by deprotonation of 3a in the presence of triphenylphosphine. Preliminary catalytic tests on the cycloisomerization of 4-pentynoic acid have underlined the impact of the pyridine sidearm on the catalytic activity.

Self-assembled M12L24 nanospheres as a reaction vessel to facilitate a dinuclear Cu(i) catalyzed cyclization reaction.

The application of large M12L24 nanospheres allows the pre-concentration of catalysts to reach high local concentrations, facilitating reactions that proceed through dinuclear mechanisms. The mechanism of the copper(i)-catalyzed cyclization of 4-pentynoic acid has been elucidated by means of a detailed mechanistic study. The kinetics of the reaction show a higher order in copper, indicating the formation of a bis-Cu intermediate as the key rate determining step of the reaction. This intermediate was further identified during catalysis by CIS-HRMS analysis of the reaction mixture. Based on the mechanistic findings, an M12L24 nanosphere was applied that can bind up to 12 copper catalysts by hydrogen bonding. This pre-organization of copper catalysts in the nanosphere results in a high local concentration of copper leading to higher reaction rates and turnover numbers as the dinuclear pathway is favored.

The phosphinoboration of 2-diphenylphosphino benzaldehyde and related aldimines

We have investigated the addition of a simple phosphinoboronate ester, Ph2PBpin (pin = 1,2-O2C2Me4), to 2-diphenylphosphinobenzaldehyde (2-Ph2PC6H4C(O)H) and related aldimine derivatives (2-Ph2PC6H4C(NR)H) as a simple and effective strategy for generating unique diphosphine ligands bearing a pendant Lewis-acid Bpin group. These reactions proceed selectively to give one new product where the phosphide fragment has added to the aldehyde (or imine) carbon atom and the electron-deficient boron group has added to the electron-rich heteroatom. Preliminary studies show these new compounds can ligate to Pd(II) and Pt(II) metal centres. These novel metal complexes, as well as the organic soluble [MCl2(coe)]2 (M = Pd, Pt, coe = cis-cyclooctene) compounds, have been shown to be effective precatalysts in the cyclisation of alkynoic acids to give the corresponding exo-dig cyclic lactones. Reactions employing these metal complexes also generated unusual endo-dig cyclic lactones not traditionally observed in these cyclisation reactions. For instance, reactions of 4-pentynoic acid also afforded significant amounts of α-angelica lactone, a biologically-important compound traditionally prepared via the catalytic dehydration and cyclisation of levulinic acid.

Preparation of a star-type telechelic macrophotoinitiator of poly(ε-caprolactone) and its use in photoinduced free radical promoted cationic polymerization

A novel and well-defined four-arm star-type telechelic macrophotoinitiator of poly(e-caprolactone) carrying benzoin photofunctional end-groups (PCL-BPI)4 was successfully synthesized by the combination of ring opening polymerization (ROP) and click chemistry techniques. First, hydroxyl end-functionalized four-arm (PCL-OH)4 was synthesized by ROP of e-caprolactone (e-CL) with pentaerythritol initiator. Then, the hydroxyl groups at the chain ends were converted to terminal alkyne groups by the condensation reaction between (PCL-OH)4 and 4-pentynoic acid to give an alkyne end-functionalized four-arm poly(e-caprolactone), (PCL-alkyne)4, as the first click couple compound. Separately, an azido end-functionalized benzoin photoinitiator (BPI-N3) was prepared in two steps to be used as the other click couple compound. (PCL-alkyne)4 and BPI-N3 were coupled via “click chemistry” to prepare a well-defined four-arm star-type telechelic macrophotoinitiator, (PCL-BPI)4. In addition, the obtained (PCL-BPI)4 macrophotoinitiator was used in the photoinitiated free radical promoted cationic polymerization of cyclohexene oxide (CHO) to produce an (AB)4-type star shaped block copolymer, (PCL-PCHO)4. All the polymers prepared were characterized by different spectral and analytical methods and their thermal behaviors were investigated.

Micro-patterns on nanocellulose films and paper by photo-induced thiol–yne click coupling: a facile method toward wetting with spatial resolution

We report a facile approach to tailor the wettability of ligno-cellulosic substrates via photo-induced thiol–yne click coupling. First, cellulosic surfaces were functionalized with 4-pentynoic acid to introduce terminal alkyne moieties for the subsequent photo-induced coupling in heterogeneous phase. Next, the (primed) surfaces were reacted with various thiol-containing molecules to systematically tailor the surface energy. Finally, the method was applied to nanocellulose films and paper to develop micro-patterned surfaces via UV lithography, endowing the substrates with thin hydrophilic channels (~ 250 μm thickness) and hydrophobic boundaries between neighboring water droplets, as small as 100 μm in width. Overall, we propose thiol-click as a facile method toward spatially-resolved wetting that enables paper-based electronics in smart labels and point-of-care bioplatforms.

Fabrication of device with poly(N-isopropylacrylamide)-b-ssDNA copolymer brush for resistivity study

In this study, we grafted bromo-terminated poly(N-isopropylacrylamide) (PNIPAAm) brushes onto thin gold films deposited on silicon, and then reacted with NaN3 to produce azido-terminated PNIPAAm brushes. A probe sequence of single-stranded DNA (ssDNA) with a 4-pentynoic acid succinimidyl ester unit was grafted onto the azido-terminated PNIPAAm brushes through a click reaction, resulting in the formation of block copolymer brushes. The PNIPAAm-b-ssDNA copolymer brushes formed supramolecular complexes stabilized by bio-multiple hydrogen bonds (BMHBs), which enhanced the proton transfer and thereby decreased the resistivity of the structures. In addition, the optimal operation window for DNA detection ranges from 0 to 0.2 M of NaCl concentration. Therefore, the specimens were prepared in the PBS solution at 150 mM NaCl concentration for target hybridization. The supramolecular complex state of the PNIPAAm-b-ssDNA copolymer brushes transformed into the phase-separated state after the hybridization with 0.5 ng/µL of its target DNA sequence owing to the competition between BMHBs and complementary hydrogen bonds. This phase transformation of the PNIPAAm and probe segments inhibited the proton transfer and significantly increased the resistivity at 25 °C. Moreover, there were no significant changes in the resistivity of the copolymer brushes after hybridization with the target sequence at 45 °C. These results indicated that the phase-separated state of the PNIPAAm-b-ssDNA copolymer brushes, which was generally occurred above the LCST, can be substantially generated after hybridization with its target DNA sequence. By performing the controlled experiments, in the same manner, using another sequence with lengths similar to that of the target sequence without complementarity. In addition, the sequences featuring various degrees of complementarity were exploited to verify the phase separation behavior inside the PNIPAAm-b-ssDNA copolymer thin film.

Mechanisms of highly stabilized ex-situ oleic acid-modified iron oxide nanoparticles functionalized with 4-pentynoic acid

In this paper, the main objective is to successfully functionalize 4-pentynoic acid on iron oxide nanoparticles (NPs) which arises second objective; to ex-situ modify different concentrations of oleic acid on the NPs. A new understanding has been achieved as to how the concentrations of oleic acid prior ex-situ modification, play a major role in the successful functionalization of 4-pentynoic acid on the NPs. The functionalization proposed is a potential alternative route of creating an acid anhydride from two carboxylic acids without the use of dehydrating agent. Unmodified NPs were synthesized by co-precipitation method and were altered to pH 12 using NH4OH to promote dispersity right before ex-situ modification with oleic acid (0.2–0.8 wt % oleic acid to iron oxide) and subsequent 4-pentynoic acid (1.63 × 10−3 mol) functionalization. Characterizations were conducted by X-ray-diffraction (XRD), Transmission Electron Microscopy (TEM), Thermogravimetric and Differential Thermal analysis (TGA-DTA), Fourier transform infrared spectroscopy (FTIR), proton nucleic magnetic resonance (NMR) and Zetasizer. A monolayer oleic acid is produced for ex-situ modification of 0.2 wt % oleic acid to iron oxide. Whereas the higher concentrations of oleic acid ex-situ modifications generate bilayer oleic acid-modified iron oxide NPs to which, functionalization of 4-pentynoic acid is only successfully performed. The samples pose highly stabilized dispersions at pH 12 varying between -42 and -75 mV, whereas the mean hydrodynamic particle size distributions are achieved at approximately 35–48 nm. Mechanisms of ex-situ modifications of different oleic acid concentrations and functionalization of 4-pentynoic acid on the iron oxide NPs at pH 12 and 333.15 K are also proposed.

Self-assembly and electrical characteristics of 4-pentynoic acid functionalized Fe3O4-γ-Fe2O3 nanoparticles on SiO2/n-Si

A novel investigation on a relationship between temperature-influential self-assembly (70–300°C) of 4-pentynoic acid functionalized Fe3O4-γ-Fe2O3 nanoparticles (NPs) on SiO2/n-Si with electrical properties was reported with the interests for metal-oxide-semiconductor applications. X-ray diffractometer (XRD) analysis conveyed that 8±1nm of the NPs were assembled. Increasing heating temperature induced growth of native oxide (SiO2). Raman analysis confirmed the coexistence of Fe3O4-γ-Fe2O3. Attenuated Total Reflectance Infrared (ATR-IR) spectra showed that self-assembly occurred via SiOC linkages. While SiOC linkages were broken down at elevated temperatures, formations of Si-OH defects were amplified; a consequence of physisorbed surfactants disintegration. Atomic force microscopy (AFM) showed that sample with more physisorbed surfactants exhibited the highest root-mean-square (RMS) roughness (18.12±7.13nm) whereas sample with lesser physisorbed surfactants displayed otherwise (12.99±4.39nm RMS roughness). Field Emission Scanning Electron Microscope (FE-SEM) analysis showed non-uniform aggregation of the NPs, deposited as film (12.6μm thickness). The increased saturation magnetization (71.527Am2/kg) and coercivity (929.942A/m) acquired by vibrating sample magnetometer (VSM) of the sample heated at 300°C verified the surfactants’ disintegration. Leakage current density-electric field (J-E) characteristics showed that sample heated at 150°C with the most aggregated NPs as well as the most developed SiOC linkages demonstrated the highest breakdown field and barrier height at 2.58×10−3 MV/cm and 0.38eV respectively. Whereas sample heated at 300°C with the least SiOC linkages as well as lesser aggregated NPs showed the lowest breakdown field and barrier height at 1.08×10−3 MV/cm and 0.19eV respectively. This study opens up better understandings on how formation and breaking down of covalent linkages as well as accumulation of defects, particularly prior temperature influential self-assembly at the interfaces, affected electrical breakdown field and barrier height. Hence, possible future development of self-assembly silicon-based metal-oxide-semiconductor (MOS) structure particularly in the presence of SiO2 can be deliberated.

Antifouling Peptide Dendrimer Surface of Monodisperse Magnetic Poly(glycidyl methacrylate) Microspheres

Antifouling properties and stability in tissue fluids are crucial for the successful application of micro- and nanoparticles in biomedicine. In this study, we prepared monodisperse magnetic poly(glycidyl methacrylate) microspheres with amino groups (mgt.PGMA-NH2) by a multistep swelling polymerization of glycidyl methacrylate (GMA). This was followed by ammonolysis of oxirane groups and precipitation of iron oxides inside the particle pores to make the microspheres magnetic. To suppress nonspecific protein adsorption from biological media, the microspheres were covered by three generations of a compact amino acid dendritic network (Ser-Lys-Ser/Lys-Ser/Lys-Ser) using peptide chemistry. The resulting particles did not aggregate under physiological conditions and contained ∼1 mmol of NH2/g that was available for further modifications. Alkyne groups accessible for click chemistry were introduced to the dendrimer-coated particles by a reaction with 4-pentynoic acid. The external particle surface and internal b...

Design of a Pd(0)-CalB CLEA Biohybrid Catalyst and Its Application in a One-Pot Cascade Reaction

Herein, a design of a biohybrid catalyst is described, consisting of Pd nanoparticles and a cross-linked network of aggregated lipase B enzyme of Candida antarctica (CalB CLEA) functioning as an active support for the Pd nanoparticles. Both entities of the hybrid catalyst showed good catalytic activity. The applicability was demonstrated in a one-pot reaction, where the Pd-catalyzed cycloisomerization of 4-pentynoic acid afforded a lactone that serves as an acyl donor in a subsequent selective enzymatic kinetic resolution of a set of sec-alcohols. The catalyst proved to be robust and could be recycled five times without a significant loss of activity.

RGDS- and TAT-Conjugated Upconversion of NaYF4:Yb(3+)/Er(3+)&SiO2 Nanoparticles: In Vitro Human Epithelioid Cervix Carcinoma Cellular Uptake, Imaging, and Targeting.

Starting NaYF4:Yb(3+)/Er(3+) nanoparticles with size tuned from 24 to 33 nm were prepared by high-temperature coprecipitation of lanthanide chlorides in high-boiling organic solvents. To enhance colloidal stability in aqueous medium, an aminosilica shell was introduced on the surface by hydrolysis and condensation of tetramethyl orthosilicate and (3-aminopropyl)trimethoxysilane using a reverse microemulsion technique; to form alkyne groups, reaction with 4-pentynoic acid followed. Finally, the cell adhesive and cell penetrating azidopentanoyl-GGGRGDSGGGY-NH2 (RGDS) and azidopentanoyl-GGGRKKRRQRRR-NH2 (TAT) peptides were conjugated to the upconversion particles via Cu(I)-catalyzed alkyne-azide cycloaddition. The concentrations of the peptides bound to the nanoparticle surfaces and amount of adsorbed residual Cu(I) catalyst were determined using an (125)I-radiolabeled RGDS peptide and a (64)Cu(I)-doped catalyst, respectively. Targeting and uptake of the RGDS- and TAT-conjugated NaYF4:Yb(3+)/Er(3+)&SiO2 nanoparticles by human cervix carcinoma HeLa cells were monitored by confocal microscopy. RGDS-conjugated nanoparticle probes were mainly localized on the cell plasma membrane due to specific binding of the peptide to the corresponding integrins. In contrast, the TAT-conjugated nanoparticles were able to cross the cell membrane and accumulate in the cell cytoplasm. Thus, this new peptide bioconjugation approach supported both extra- and intracellular nanoparticle uptake, enabling targeting and imaging of the specific tumor phenotypes.

A new unsymmetrical phthalocyanine with a single o-carborane substituent

Unsymmetrical zinc phthalocyanine carrying a single o-carborane substituent on the peripheral position was synthesized in a multistep reaction sequence. At the first step, metal-free phthalocyanine 3 was prepared by cyclotetramerization of 4,5-di(hexylthio)phthalonitrile and 4-(2-hydroxyethylthio)phthalonitrile in pentanol in the presence of lithium; and zinc phthalocyanine 4 was prepared by insertion of Zn(II) salt. After esterification of phthalocyanine 4 with 4-pentynoic acid, terminal alkynyl bearing precursor phthalocyanine 5 was obtained. At the last step, reaction of decaborane with phthalocyanine 5 yielded phthalocyanine 6 with the desired o-carborane moiety. The new phthalocyanine compounds were characterized by elemental analysis, NMR, FT-IR, UV–vis and mass spectral data. Aggregation behaviour and electrochemical properties of these newly synthesized unsymmetrical phthalocyanine derivatives were also reported.

Construction of Double-Eight and Double-Trefoil Polymer Topologies with Core-Clickable kyklo-Telechelic Precursors

A dicyclic, eight-shaped and a tricyclic, trefoil-shaped poly(THF) both having an alkyne group at the core position (II and III, respectively) have been introduced as versatile core-clickable kyklo-telechelic precursors. The prepolymer II has been prepared by an ESA-CF (electrostatic self-assembly and covalent fixation) process using an assembly (1a/2b), composed of two units of linear poly(THF) having N-phenylpyrrolidinium salt groups carrying one unit of a tetrafunctional carboxylate having an alkyne group as a counteranion. Alternatively, the prepolymer III has been produced through a click process using a cyclic poly(THF) precursor having an azide group (Ia), obtainable also by the ESA-CF technique, with a tripropargylated pentaerythritol derivative (2c) followed by the esterification with 4-pentynoic acid to introduce again an alkyne group. The subsequent click coupling reaction of II and III with a linear telechelic poly(THF) having azide groups (1b) afforded successfully novel tetra- and hexacyclic...