Pendant Pyridine Research Articles

Facile Synthesis of Amphiphilic Bottlebrush Block Copolymers Bearing Pyridine Pendants via Click Reaction from Protected Alkyne Side Groups

We present the facile synthetic platform for the production of amphiphilic bottlebrush block copolymers bearing pyridine pendants through combination of living anionic polymerization (LAP), ring-op...

Glass transition analysis of model metallosupramolecular polyesters bearing pendant pyridine ligands with a controlled ligand–ligand distance

Supramolecular materials formed via metal-ligand coordination, so-called metallosupramolecular materials, have attracted attention due to their ability to modify a broad range of physical properties depending on the association strength at the coordination bond. Here, we demonstrate the correlation between the glass transition properties and the ligand distance by utilizing amorphous polyesters (denoted as PE-Py) with pendant pyridine ligands arranged homogeneously along the chain. The ligand distance is treated as the pyridine group equivalent molecular weight (MPy) and takes values of 900, 750, 550, and 420. The metal salt ZnCl2 forms coordination bonds with the pyridine ligands, generating a metallosupramolecular network. The fraction of coordinated pyridine is finely tuned by the mole ratio between the pyridine ligand and ZnCl2 ([Zn2+]/[Py]) while adhering to the stoichiometric rule. DSC measurements reveal that the variation in the glass transition temperature (Tg) with increasing [Zn2+]/[Py] is closely correlated with 1/MPy. Temperature-ramp rheological measurements are also performed, revealing that the apparent activation energy (Ea) of segmental motion has a quasi-linear relationship with 1/MPy. Thus, the present study demonstrates that the degree of restriction for segmental motion is very systematically strengthened as the ligand distance decreases, highlighting the importance of ligand distance in physical property control of metallosupramolecular materials. We here demonstrate the importance of ligand–ligand distance on physical property tuning of metallosupramolecular materials by utilizing model-like polyesters bearing pyridine ligands at the side groups with a controlled ligand-distance. The ligand distance is treated as the pyridine group equivalent molecular weight (MPy) and takes values of 900, 750, 550, and 420. The metal salt ZnCl2 forms coordination bonds with the pyridine ligands, generating a metallosupramolecular network. DSC and rheological measurements revealed that the glass transition temperatures and apparent activation energy (Ea) of segmental motion changes in a close correlation with 1/MPy.

One-pot synthesis of dual supramolecular associative copolymers by using a novel acrylate monomer bearing urethane and pendant pyridine groups

A highly efficient, one-pot synthesis of dual supramolecular associative copolymers is demonstrated by utilizing a novel acrylate monomer bearing urethane and pendant pyridine groups.

Efficient Photocatalytic CO2 Reduction by a Ni(II) Complex Having Pyridine Pendants through Capturing a Mg2+ Ion as a Lewis-Acid Cocatalyst.

We have synthesized a new Ni(II) complex having an S2N2-tetradentate ligand with two noncoordinating pyridine pendants as binding sites of Lewis-acidic metal ions in the vicinity of the Ni center, aiming at efficient CO production in photocatalytic CO2 reduction. In the presence of Mg2+ ions, enhancement of selective CO formation was observed in photocatalytic CO2 reduction by the Ni complex with the pyridine pendants through the formation of a Mg2+-bound species, as compared to the previously reported Ni complex without the Lewis-acid capturing sites. A higher quantum yield of CO evolution for the Mg2+-bound Ni complex was determined to be 11.1%. Even at lower CO2 concentration (5%), the Ni complex with the pendants exhibited comparable CO production to that at the CO2-saturated concentration (100%). The Mg2+-bound Ni complex was evidenced by mass spectrometry and 1H NMR measurements. The enhancement of CO2 reduction by the Mg2+-bound species should be derived from cooperativity between the Ni and Mg centers for the stabilization of a Ni-CO2 intermediate by a Lewis-acidic Mg2+ ion captured in the vicinity of the Ni center, as supported by DFT calculations. The detailed mechanism of photocatalytic CO2 reduction by the Ni complex with the pyridine pendants in the presence of Mg2+ ions is discussed based on spectroscopic detection of the intermediate and kinetic analysis.

In situ Investigations of a Proton Trap Material: A PEDOT-Based Copolymer with Hydroquinone and Pyridine Side Groups Having Robust Cyclability in Organic Electrolytes and Ionic Liquids

A conducting redox polymer based on PEDOT with hydroquinone and pyridine pendant groups is reported and characterized as a proton trap material. The proton trap functionality, where protons are tra...

Synthesis and photodynamic activity of novel non-symmetrical diaryl porphyrins against cancer cell lines

Photodynamic therapy (PDT) of cancer uses photosensitizers (PS), a light source and oxygen to generate high levels of reactive oxygen species (ROS), that exert a cytotoxic action on tumor cells. Recently, it has been shown that mixed non-symmetrical diaryl porphyrins, with two different pendants, are more photodynamically active than symmetrical diaryl porphyrins.In the present study, we investigate the in vitro photodynamic effects of four novel non-symmetrical diaryl porphyrins, two of which bear one pentafluoro-phenyl and one bromo-alkyl (apolar) pendant, whereas the two others bear one pentafluoro-phenyl and one cationic pyridine pendant. The four compounds were tested in a small panel of human cancer cell lines, and their photodynamic activities were compared with that of m-THPC (Foscan), currently the most successful PS approved for clinical use in cancer PDT.The results of the cytotoxicity studies indicate that the two molecules bearing the cationic pendant are more potent in vitro than those with the apolar pendant, and that they are as potent as Foscan. To gain further insights into the mechanism of PS-induced phototoxicity, induction of apoptotic, autophagic and necrotic cell death, and generation of reactive oxygen species (ROS) were evaluated in cancer cells following exposure to the PSs and irradiation. The effect of the PSs on the migratory activity of the cells was also assessed.The data obtained from this work support a greater potency of diaryl porphyrins with a positive charge in inducing cell death, as compared to those with the bromo-alkyl pendant; most importantly, some of these novel compounds exhibit features that might make them superior to the clinically approved PS Foscan.

Functionalizable, Side Chain-Immolative Poly(benzyl ether)s.

Herein, we report a poly(benzyl ether)-based self-immolative polymer (SIP) with pendant pyridine disulfide groups. Cleavage of the side-chain disulfides leads to the formation of phenolates, which initiate depolymerization from the side chain. Due to the higher density of the disulfide groups compared to that of the chain-end-capping group, which normally is responsible for initiating depolymerization of SIPs, the side chain-immolative polymer (ScIP) can be readily degraded in the solid state where the mobility of polymer chains is substantially limited. The ScIP was also further modified through the thiol-disulfide exchange reaction to prepare ScIP-g-poly(ethylene glycol) graft polymers and organogels, which were also able to undergo complete reductive self-immolative degradation.

Crystal structure of NiFe(CO)5[tris(pyridyl-meth-yl)aza-phosphatrane]: a synthetic mimic of the NiFe hydrogenase active site incorporating a pendant pyridine base.

The reaction of Ni(TPAP)(COD) {where TPAP = [(NC5H4)CH2]3P(NC2H4)3N} with Fe(CO)5 resulted in the isolation of the title heterobimetallic NiFe(TPAP)(CO)5 complex di-μ-carbonyl-tricarbon-yl[2,8,9-tris-(pyridin-2-yl-meth-yl)-2,5,8,9-tetra-aza-1-phosphabi-cyclo-[3.3.3]undeca-ne]ironnickel, [FeNi(C24H30N7P)(CO)5]. Characterization of the complex by 1H and 31P NMR as well as IR spectroscopy are presented. The structure of NiFe(TPAP)(CO)5 reveals three terminally bound CO mol-ecules on Fe0, two bridging CO mol-ecules between Ni0 and Fe0, and TPAP coordinated to Ni0. The Ni-Fe bond length is 2.4828 (4) Å, similar to that of the reduced form of the active site of NiFe hydrogenase (∼2.5 Å). Additionally, a proximal pendant base from one of the non-coordinating pyridine groups of TPAP is also present. Although involvement of a pendant base has been cited in the mechanism of NiFe hydrogenase, this moiety has yet to be incorporated in a structurally characterized synthetic mimic with key structural motifs (terminally bound CO or CN ligands on Fe). Thus, the title complex NiFe(TPAP)(CO)5 is an unique synthetic model for NiFe hydrogenase. In the crystal, the complex mol-ecules are linked by C-H⋯O hydrogen bonds, forming undulating layers parallel to (100). Within the layers, there are offset π-π [inter-centroid distance = 3.2739 (5) Å] and C-H⋯π inter-actions present. The layers are linked by further C-H⋯π inter-actions, forming a supra-molecular framework.

Polymorphic self-assembly of pyrazine-based tectons at the solution-solid interface.

Exploring the surface self-assembly of small molecules that act as building blocks (tectons) for complex supramolecular structures is crucial for realizing surface-supported functional molecular devices. Here, we report on the synthesis and surface self-assembly of a new pyrazine-derived molecule with pyridine pendants. Ambient scanning tunneling microscopy investigation at the solution–solid interface reveals polymorphic self-assembly of these molecules on a HOPG substrate. Two different molecular packing structures with equal distribution are observed. Detailed analysis of the STM images emphasizes the crucial role of weak intermolecular hydrogen bonding, and molecule–substrate interactions in the formation of the observed polymorphs. Such weak hydrogen bonding interactions are highly desirable for the formation of modular supramolecular architectures since they can provide sufficiently robust molecular structures and also facilitate error correction.

Design and photophysical studies of iridium(iii)-cobalt(iii) dyads and their application for dihydrogen photo-evolution.

We report several new dyads constituted of cationic iridium(iii) photosensitizers and cobalt(iii) catalyst connected via free pendant pyridine on the photosensitizers. These dyads were studied by X-ray crystallography, electrochemistry, absorption and emission spectroscopy as well as theoretical calculations and were shown to efficiently produce H2 under visible light irradiation. In every case, the dyad outperformed the equivalent system without a pendant pyridine. The dependence between irradiation wavelength and photocatalytic performances was also studied, with H2 being evolved with turn-over numbers up to 295, 251, 188 and 78 molH2 molPS-1 under blue, green, yellow and red light, respectively.

Structure of the CoI Intermediate of a Cobalt Pentapyridyl Catalyst for Hydrogen Evolution Revealed by Time-Resolved X-ray Spectroscopy.

Cobalt polypyridyls are highly efficient water-stable molecular catalysts for hydrogen evolution. The catalytic mechanism explaining their activity is under debate and the main question is the nature of the involvement of pyridyls in the proton transfer: the pentapyridyl ligand, acting as a pentadentate ligand, can provide stability to the catalyst or one of the pyridines can be involved in the proton transfer. Time-resolved Co K-edge X-ray absorption spectroscopy in the microsecond time range indicates that, for the [CoII (aPPy)] catalyst (aPPy=di([2,2'-bipyridin]-6-yl)(pyridin-2-yl)methanol), the pendant pyridine dissociates from the cobalt in the intermediate CoI state. This opens the possibility for pyridinium to act as an intramolecular proton donor. In the resting state, the catalyst returns to the original six-coordinate high-spin CoII state with a pentapyridyl and one water molecule coordinating to the metal center. Such a bifunctional role of the polypyridyl ligands can be exploited during further optimization of the catalyst.

A Smorgasbord of 17 Cobalt Complexes Active for Photocatalytic Hydrogen Evolution.

Seventeen cobalt complexes-eleven dinuclear cobalt(II) complexes and three tetranuclear cobalt complexes (two mixed valent) of ditopic ligands, with varying N-donor aromatic bridging moieties and pendant pyridine side arms, as well as three mononuclear cobalt(II) complexes of Schiff base macrocyclic ligands-have been screened for photocatalytic hydrogen evolution reaction (HER) activity. All 17 complexes are active catalysts for the HER, in both DMF and aqueous solution, in tandem with the [Ru(bpy)3 ]2+ (bpy=2,2'-bipyridine) photosensitiser. All are benchmarked to the literature standard [CoIII (dmgH)2 (py)Cl] (dmg=dimethylglyoxime, py=pyridine) under identical conditions. Two families of dinuclear cobalt(II) complexes of bis-tetradentate ligands that provide a triazole bridging moiety and mononuclear cobalt(II) complexes of tetradentate Schiff base macrocycles were found to be the most active catalysts, outperforming [CoIII (dmgH)2 (py)Cl] by two- to three-fold. Within these two families, the use of shorter alkyl linkers between the N donors, and hence, smaller chelate ring sizes, was found to significantly enhance catalytic performance, whereas the variation of peripheral functional groups was found to have little effect. This last point will be convenient for subsequent surface immobilisation studies.

Synthesis, characterisation and protonation of phosphate disubstituted derivatives with pyridyl-functionalized diiron

Abstract Three new phosphine disubstituted derivatives of [2Fe2S] model complexes with pendant pyridine family, [(μ-SEt)(μ-SCH2C6H4N)Fe2(CO)4(L)2] (2, L = PPh3; 3, L = dppm; 4, L = PMe3), have been synthesized and the molecular structure of 2 was determinated by single crystal X-ray diffraction analysis. They were all characterized by MS, FT-IR, 31P and 1H NMR spectra and their electrochemical behaviors were also conducted. The protonation of complex 4 with HBF4·Et2O was also investigated by FT-IR, 31P and 1H NMR spectroscopies at variable temperature, which reveals the formations of both bridging and terminal hydride intermediates.

A Series of Lithium Pyridyl Phenolate Complexes with a Pendant Pyridyl Group for Electron-Injection Layers in Organic Light-Emitting Devices.

We report a new series of lithium pyridyl phenolate complexes with a pendant pyridyl group, Li2BPP, Li3BPP, and Li4BPP, in which the pendant pyridines are substituted at the 2-, 3-, and 4-positions, respectively. The most important difference between these complexes is their molecular planarity; Li3BPP and Li4BPP adopt twisted bipyridine structures, whereas Li2BPP adopts a planar structure owing to the steric hindrance and chelating effect of bipyridine on the Li core. The planar structure leads to crystallization through π-π stacking interactions, and the small differences in the molecular structures of the pendant pyridine rings cause drastic differences in the physical properties of thin solid films of these complexes. We applied these complexes as electron-injection layers (EILs) in Ir(ppy)3-based organic light-emitting devices. When thin EILs were used, Li3BPP and Li4BPP afforded lower driving voltages than Li2BPP; the order of the driving voltages followed the order of their electron affinity values. Moreover, the dependence of driving voltage on the EIL thickness was investigated for each complex. Among the three LiBPP derivatives, Li2BPP-based devices showed almost negligible EIL thickness dependence, which may be attributable to the high crystallinity of Li2BPP. All LiBPP-based devices also showed higher stability than conventional 8-quinolinolato lithium-based devices.

Targeted structural modification of spin crossover complexes: pyridine vs pyrazine

2-(Aminomethyl)pyrazine has been prepared in five steps from 2-pyrazine carboxylic acid. From this key amine, two new bis-terdentate triazole-based ligands which feature pendant pyrazine groups, PZMAT and PZMPT (4-amino- and 4-pyrrolyl-3,5-bis{[(2-pyrazylmethyl)amino]methyl}-4H-1,2,4-triazole, respectively), and two dinuclear complexes of them, [FeII2(PZMAT)2](BF4)4∙MeOH∙2H2O (1∙MeOH∙2H2O) and [FeII2(PZMPT)2](BF4)4∙3H2O (2∙3H2O), have been prepared. A structure determination at 100 K on 2∙3.5MeCN confirmed that the ligands adopt the expected binding mode, providing all twelve donors to the two iron(II) centres and two N1,N2-triazole bridges between them. Both undergo gradual incomplete spin transitions: at room temperature 1∙MeOH∙2H2O and 2∙3H2O are approximately two-thirds to three-quarters [HS-HS], dropping to mostly ‘[HS-LS]’ at 50 K. The structure determination and Mössbauer spectroscopy of 2 qualitatively support this. These findings are consistent with the pendant pyrazines providing a somewhat higher field strength than the pendant pyridines do in the analogous PMRT complexes.

Pyrazine based Pt(II) bis‐alkynyl organometallic complexes: Synthesis, characterization, and cytotoxic effect on A549 human lung carcinoma cells

A facile and efficient synthesis of a series of five new pyrazine‐based organometallic complexes is being reported. The complexes (2–6) have been fully characterized. Molecules 2, 3 and 6 were structurally characterized by single crystal X‐ray crystallographic analyses. Additionally, anticancer properties of these organometallic complexes have been studied against A549 human lung carcinoma cells. Biological studies suggest that complex 5 (with pendant pyridine moieties) exhibited maximal growth inhibitory cytotoxic effect even at lower concentration (nearly 0.5–1 μM) whereas the other four compounds (2, 3, 4 and 6) were non‐toxic below 1 μM concentration. Two complexes (4 and 6) were effective only at higher doses (approx 30 μM) while the remaining two organometallic complexes (2 and 3) were able to inhibit 50% cell growth at slightly lower concentration (nearly 10 μM). As far as IC50 is concerned, 5 exhibited a minimum value ranging between 3–5 μM which is comparable with cisplatin under similar conditions.

Synthesis and electro-optical properties of fluorene containing blue luminescent rod-coil homopolymers with pendant pyridine

Abstract Two well defined, blue luminescent homopolymers containing 9,9-diethylfluorene core with electron withdrawing pendant pyridine, Suzuki-coupled with the corresponding borolane of decoxy phenyl (PFPA) and naphthalene (PFNA) have been designed and synthesized efficiently. The obtained rod-coil polymers have the average molecular weight of 15212 (PFPA) and 15130 (PFNA) with polydispersity indices (PDIs) 1.07 and 1.3, respectively. The polymers have good solubility and high thermal stability with the decomposition temperature of 362 °C (PFPA) and 367 °C (PFNA) correspondingly. Furthermore the optical and electrochemical properties of the polymers have been investigated. The polymers exhibited photoluminescence (PL) maxima at 410 nm (PFPA) and 414 nm (PFNA) excited at 340 nm, as stable blue luminescence polymers at low concentration of 10−6 M with a quantum yield of 0.64 and 0.62, respectively. In addition the annealed (150 °C) polymer films showed better stability of its photoluminescence spectra. Absorbance and fluorescence emission spectra of PFPA and PFNA were compared in order to evaluate the effects of substituent, phenyl and naphthalene in pyridine pendant fluorene moieties.

A stretchable polysiloxane elastomer with self-healing capacity at room temperature and solvatochromic properties.

A stretchable silicon elastomer comprising cobalt ions in pyridine pendant polydimethylsiloxane (PDMS) was prepared. Different from previously reported cobalt-coordinated elastomers, these elastomers are self-healable at room temperature with a high healing efficiency of over 90%. Besides, they exhibit tailored solvatochromic properties over a wide range without sacrificing its self-healing ability at room-temperature.

New polytriazoleimides containing green synthesized titanium dioxide using Artemisia pallens plant extract: optical, dielectric, thermal and mechanical properties

A novel aromatic diamine containing a pyridine pendant group, 1,2,3-triazole ring and ether linkage was synthesized by ‘click reaction’ in the presence of Cu(i) catalyst.

Reprint of: Pt(II) pyridinium amidate (PYA) complexes: Preparation and in vitro anticancer activity studies

N-[1-Alkylpyridin-4(1H)-ylidene]amides (PYAs), also known as pyridinium amidates, are a class of recently introduced ligands for transition metal ions. Herein we report the synthesis of the Pt(PYA) complexes [PtCl(DMSO)(HL)]Cl2 (1), [Pt(CH3)(DMSO)(L)]Cl (2) and [Pt(CH3)(PPh3)(L)]Cl (3) (L=N-(1-benzylpyridin-4(1H)-ylidene)picolinamide). L and [HL]+ act as bidentate ligands coordinating through the pendant pyridine and either the amidate oxygen or nitrogen atoms to give the corresponding N,O or N,N linkage isomers. DFT calculations were carried out to determine the most energetically favorable isomeric forms of these compounds. For 1 the N,O coordination mode was lower in energy, while for 2 and 3 hardly any difference was found. In vitro cytotoxicity studies of [HL]Cl and 1 in human colorectal carcinoma HCT116, non-small cell lung carcinoma NCI-H460, and cervical carcinoma SiHa cells showed that both compounds are cytotoxic in the low μM range.