Bridging Nitrogen Atoms Research Articles

1,4-diaminophthalazine complexes of Re(CO)3

1,3-Diiminoisoindolines and substituted variants react with hydrazine to produce 1,4-diaminophthalazines. In this paper, we present the chemistry of 1,4-diaminophthalazine and two modified versions with the Re(CO)3 unit. The 1,4-diaminophthalazine ligand forms a bimetallic complex similar to that seen with unmodified phthalazine. In contrast, the semihemiporphyrazine-derived chelating ligands bind Re(CO)3 as neutral bidentate compounds; the freebase pyrazole and indazole modified 1,4-diaminophthalazines exhibit multiple tautomerization states with ionizable protons. Notably, protonation of the meso bridging nitrogen atom reduces the degree of conjugation between the two halves of the chelate, resulting in a diimine-like complex that lacks significant absorption in the visible spectrum due to the abrogation of the low energy metal to ligand charge transfer (MLCT) transition.

A Neutral Pyridine-Pyrazole-Based N^N*N^N Ligand as a Tetradentate Chromophore for Diverse Transition Metal Cations

Herein, the synthesis and the structural as well as the photophysical characterization of five transition metal complexes bearing a neutral pyridine-pyrazole-based N^N*N^N ligand (L) acting as a tetradentate chelator are reported. The luminophore can be synthesized via two different pathways. An alkyl chain with a terminal tert-butyl moiety was inserted on the bridging nitrogen atom to enhance the solubility of the complexes in organic solvents. Due to the neutral character of L, metal ions with different charges and electronic configurations can be chelated. Thus, complexes with Pt(II) (C1), Ag(I) (C2), Zn(II) (C3), Co(II) (C4) and Fe(II) (C5) were synthesized. Single-crystal X-ray diffraction experiments showed that complex C2 exhibits a completely different structure in the crystalline state if compared with C3 and C5, i.e., depending on the chelated cation. The UV-vis absorption and the NMR spectra showed that the complexes dissociate in liquid solutions, except for the Pt(II)-based coordination compound. Therefore, the photophysical properties of the complexes and of the ligand were studied in the solid state. For the Pt(II)-based species, a characteristic metal-perturbed ligand-centered phosphorescence was traceable, both in dilute solutions as well as in the solid state.

Molten salt Cu(I) intercalation into the poly(triazine imide) for the electrochemical sensing of nitrite

AbstractSlight modification of the molten salt synthesis of poly(triazine imide) (PTI) with introduction of copper (I) chloride yielded a novel copper modified material. Energy‐dispersive x‐ray spectroscopy together with electron microscopy confirmed homogenous distribution of the copper within PTI lattice. X‐ray photoelectron spectroscopy suggests the copper to coordinate randomly at bridging nitrogen atoms. Thus obtained material exhibited excellent sensitivity to nitrite anions together with low limits of detection. Under previously optimized experimental conditions and pH 4 of supporting electrolyte, differential pulse voltammetric detection method showed linear response in wide range from 5 to 2200 μM with detection limit of 1.3 μM. Practical applicability for the developed method was scrutinized in wastewater and pipe water samples. Developed method of metal ion intercalation open doors to widespread introduction of metal ions in the PTI structure for practical utilization.

Синтез и электрофильная гетероциклизация 3 алкенилсульфанил-5-фенил-1,2,4-триазинов под дейст-вием иода и брома

Derivatives of 1,2,4-triazine-3-thione are interesting research objects due to a wide range of their applications: drugs, optical substances, precursors for synthesis of new pyridine systems by the Diels-Alder reaction. In the present study, using alkylation of 5-phenyl-2,3-dihydro-1,2,4-triazine-3-thione (1) by 3-chloro-2-methyl-propene, 2,3-dibromopropene-1, 1-bromo-3-methylbut-2-ene and 4-brombut-1-ene, we have obtained 3-(2-methylprop-1-enyl)-, 3-(2-bromoprop-1-enyl)-, 3-prenylsulfanyl- and 3-butenylsulfanyl-5-phenyl-1,2,4-triazines (2a-d), previously unknown. In the 1H NMR spectrum of compound 2b, the shifts of the signal of pro-tons of the SCH2 group and the signal of protons of the vinyl group into a weak field by 0.48 ppm and 0.60 ppm can be observed, compared to the similar signals in the spectrum of 3-allylsulfanyl-5-phenyl-1,2,4-triazine. This may be due to the bromine atom in the allyl fragment. The weakest-field signal in the 13C NMR spectra of compounds 2a-d in the region of 171.86–173.68 ppm refers to the aromatic carbon atom of the triazine cycle in the third position (C-3), bound to a sulfur atom and two nitrogen atoms. New condensed heterocyclic systems of ionic type with a bridging nitrogen atom have been synthesized by electrophilic heterocyclization of methallyl-, bromallyl-, prenyl- and butenyl sulfides 2a-d. At the same time, [1,3]thiazolo[3,2-b][1,2,4]triazinium halides have been obtained by heterocyclization of compounds 2a,2b, and [1,3]thiazino[3,2–b][1,2,4]triazinium halides have been produced by heterocyclization of com-pounds 2c,2d. In the 1H NMR spectra of triazinium halides, a characteristic shift of the signal of the H-6 aromatic proton to the weak field region is observed in comparison with the similar sig-nal in the spectrum of the initial 2a-d sulfides. In the 13C NMR spectra of triazinium halides, there is a shift in the signal of the aromatic carbon atom associated with a sulfur atom and two nitrogen atoms (in the region of 162.56-172.42 ppm), which can be explained by the appearance of a positively charged nitrogen atom in their structure.

Pyrazole and Indazole Semihemiporphyrazine Complexes of Rhenium Tricarbonyl: A Structure/Properties Study

AbstractThe semihemiporphyrazines are a class of ligands comprised of a heterocycle ring and an isoindoline unit linked through a bridging nitrogen atom. These bidentate ligands can be altered in the exocyclic heteroatom position on the isoindoline and in the identity of the heterocycle. Herein, we present a series of Re(CO)3X (X=Cl, Br, py) complexes of indazole and pyrazole‐based semihemiporphyrazines. Changing the ligand and the axial position at the metal alters the character of the complexes, including the structure, tautomerization and charge of the chelate. Modifications to the semihemiporphyrazine also alter the electronic structure of the resultant Re(CO)3 complexed as demonstrated in their UV‐visible spectra. In addition to full characterization, we carried out density functional theory (DFT) and time‐dependent density functional theory (TDDFT) to interrogate the electronic structures of these compounds.

Probing fluorination promoted sodiophilic sites with model systems of F16CuPc and CuPc

Sodium metal batteries (SMBs) are receiving broad attention due to the high specific capacity of sodium metal anodes and the material abundance on earth. However, the growth of dendrites results in poor battery performance and severe safety problems, inhibiting the commercial application of SMBs. To stabilize sodium metal anodes, various methods have been developed to optimize the solid electrolyte interphase (SEI) layer and adjust the electroplating/stripping behavior of sodium. Among the methods, developing anode host materials and adding electrolyte additives to build a protective layer are promising and convenient. However, the understanding of the interaction process between sodium metal and those organic materials is still limited, but is essential for the rational design of advanced anode hosts and electrolyte additives. In this study, we use copper(II) hexadecafluorophthalocyanine (F16CuPc), and copper(II) phthalocyanine (CuPc), as model systems to unravel the sodium interaction with polar functional groups by in-situ photoelectron spectroscopy and density functional theory (DFT) calculations. It is found that sodium atoms prefer to interact with the inner pyrrolic nitrogen sites of CuPc, while they prefer to interact with the outer aza bridge nitrogen atoms, owing to Na-F interaction at the Na/F16CuPc interface. Besides, for the both organic molecules, the central Cu(II) ions are reduced to Cu(I) ions by charge transfer from deposited sodium. The fluorine-containing groups are proven to promote the interaction process of sodium in organic materials, which sheds light on the design of functional interfaces in host materials and anode protective layers for sodium metal anodes.Graphical

Nitrogen-bridged star-shaped fused-ring electron acceptors for organic solar cells

Two kinds of nitrogen-bridged star-shaped fused-ring electron acceptors based on benzo[1,2-b:3,4-b’-5,6-b’’]tri(4-H-dithieno[3,2-b:2’,3’-d]pyrrole) (BTDTP) core with linear and branched alkyl side chains on bridging nitrogen atoms are developed. Both electron acceptors exhibit strong intramolecular charge transfer absorption bands at 500–800 nm (molar extinction coefficient of 3.0 × 105 M −1 cm−1) with narrow optical bandgaps around 1.58 eV, but reveal different molecular packing and morphology. Compared to acceptor with linear side chains, the acceptor bearing branched side chains exhibits ordered face-on orientation with tight π-π stacking, as well as more favorable phase separation morphology and balanced charge transport when blended with polymer donor PM6. Organic solar cell device based on acceptors bearing branched side chains achieves a power conversion efficiency (PCE) of 9.95% with a fill factor of 74.98% and a short-circuit current density of 14.90 mA cm−2, which is much superior to the device using acceptors bearing linear side chains (a PCE of 6.74%).

A robust polyfunctional Pd(II)-based magnetic amphiphilic nanocatalyst for the Suzuki\u2013Miyaura coupling reaction

Herein, a robust Pd(II)-based polyfunctional magnetic amphiphilic artificial metalloenzyme was prepared by anchoring a Pd(2,2′-dipyridylamine)Cl2 bearing hydrophilic monomethyl ether poly(ethylene glycol) (mPEG) chains on the surface of amino-functionalized silica-coated magnetic nanoparticles. The 2,2′-dipyridylamine (dpa) has shown excellent complexation properties for Pd(II) and it could be easily anchored onto functionalized magnetic support by the bridging nitrogen atom. Moreover, the bridging nitrogen atom at the proximity of Pd(II) catalytic center could play an important role in dynamic suppramolecular interactions with substrates. The leaching, air and moisture resistant [Pd(dpa)Cl2] complex endow the dynamic and robust structure to the designed artificial enzyme. Moreover, the water dispersibility of designed artificial metalloenzyme raised from mPEG chains and the magnetic nanoparticles core which could function as protein mimics endow it other necessary characters of artificial enzymes. The prepared artificial metalloenzyme displayed remarkable activity in Suzuki–Miyaura cross-coupling reaction employing low-palladium loading under mild conditions, with the exceptionally high turnover frequency, clean reaction profile, easy work-up procedure, good to excellent products yields and short reaction times. The designed air- and moisture-stable artificial metalloenzyme could recycle more than fifteen times with easy separation procedure in aqueous solution under aerobic conditions without any noticeable loss in activity.

Discovery of a novel series of GPR119 agonists: Design, synthesis, and biological evaluation of N-(Piperidin-4-yl)-N-(trifluoromethyl)pyrimidin-4-amine derivatives

We undertook an optimization effort involving propan-2-yl 4-({6-[5-(methanesulfonyl)-2,3-dihydro-1H-indol-1-yl]pyrimidin-4-yl}oxy)piperidine-1-carboxylate 1, which we had previously discovered as a novel G protein-coupled receptor 119 (GPR119) agonist. To occupy a presumed hydrophobic space between the pyrimidine and piperidine rings in interaction with GPR119, we replaced the linker oxygen with nitrogen. Subsequently, the introduction of a substituent at the bridging nitrogen atom was explored. We found that the installation of N-trifluoromethyl group 10 not only enhanced GPR119 agonist activity but also considerably improved the human ether-à-go-go-related gene (hERG) inhibition profile. These improvements were not observed for non-fluorinated substituents, such as ethyl analog 8b. The next optimization effort focused on the exploration of a new surrogate structure for the indoline ring and the isosteric replacements of the piperidine N-Boc group to improve solubility, metabolic stability, and oral bioavailability. As a result, N-{1-[3-(2-fluoropropan-2-yl)-1,2,4-oxadiazol-5-yl]piperidin-4-yl}-6-{[1-(methanesulfonyl)piperidin-4-yl]oxy}-N-(trifluoromethyl)pyrimidin-4-amine (27) was identified as a potent and orally bioavailable GPR119 agonist. This compound augmented insulin secretion and effectively lowered plasma glucose excursion in a diabetic animal model after oral administration. In this study, we discuss the designs, syntheses, and biological activities of a novel series of N-(piperidin-4-yl)-N-(trifluoromethyl)pyrimidin-4-amine derivatives as GPR119 agonists, and to determine the distinctive effect of the N-trifluoromethyl group on hERG inhibition, we also discuss the conformational preference of representative compounds.

Linear and nonlinear optical response of g-C3N4-based quantum dots* *Project supported by the National Key R&D Program of China (Grant No. 2017YFA0303600), the National Natural Science Foundation of China (Grant No. 11974253), and Science Speciality Program of Sichuan University (Grant No. 2020SCUNL210).

Graphite carbon nitride (g-C3N4) attracts wide-ranging research interest due to its extraordinary physicochemical properties and promising applications ranging from heterogeneous catalysis to fuel cells. In this work, we design different g-C3N4-based quantum dots (gCNQDs), carry out a systematic study of optical properties, and elucidate the shape selectivity, composite nanostructure, and outfield effect. In particular, composites of gCNQDs and metal nanochains present excellent optical response, making it applicable to bioimaging, nano-plasma devices, and metalloenzyme in infrared light related fields. Besides, QDs which original bridging nitrogen atoms are replaced by amino (–NH2), hydroxyl (–OH), and methyl (–CH3) functional groups respectively, have excellent spectral selectivity in the deep ultraviolet region. More interestingly, in the study of the laser interaction with materials, the gCNQDs exhibit extremely high stability and light corrosion resistance. Phase transition from insulation to metal is observed under the critical condition of about 5 eV intensity or 337 nm wavelength. All provided theoretical support for designs and applications in g-C3N4 quantum devices.

2,4,9‐Triazaadamantanes with “Clickable” Groups: Synthesis, Structure and Applications as Tripodal Platforms

2,4,9‐Triazaadamantanes (TRIADs) are promising yet scarcely available, conformationally rigid platforms for potential applications in the design of functional molecules and materials. Here, we report a facile synthesis of various N‐ and C7‐substituted 2,4,9‐triazaadamantanes, starting from amines and 4‐allylhepta‐1,6‐dienes. A focus was placed on the synthesis of 2,4,9‐triazaadamantanes bearing reactive groups (NH2, propargyl, OH) on the bridge nitrogen atoms, which were then used to decorate the 3D scaffold by hydrazone, triazole, and boronate linkages. A reversible opening of the adamantane cage to the acyclic tris‐oxime form was observed for 2,4,9‐triazaadamantanes possessing hydroxy‐groups on the nitrogen atoms (TRIAD‐triols). This process could be controlled by temperature or by complexation of TRIAD‐triol with a boronic acid. The structure of 2,4,9‐triazaadamantanes and the stereodynamics at the bridge nitrogen atoms were studied by X‐ray analysis and DFT calculations.

Synthetic Control of Quantum Interference by Regulating Charge on a Single Atom in Heteroaromatic Molecular Junctions.

A key area of activity in contemporary molecular electronics is the chemical control of conductance of molecular junctions and devices. Here we study and modify a range of pyrrolodipyridines (carbazole-like) molecular wires. We are able to change the electrical conductance and quantum interference patterns by chemically regulating the bridging nitrogen atom in the tricyclic ring system. A series of eight different N-substituted pyrrolodipyridines has been synthesized and subjected to single-molecule electrical characterization using an STM break junction. Correlations of these experimental data with theoretical calculations underline the importance of the pyrrolic nitrogen in facilitating conductance across the molecular bridge and controlling quantum interference. The large chemical modulation for the meta-connected series is not apparent for the para-series, showing the competition between (i) meta-connectivity quantum interference phenomena and (ii) the ability of the pyrrolic nitrogen to facilitate conductance, that can be modulated by chemical substitution.

Metal-free carbon nitride with boosting photo-redox ability realized by the controlled carbon dopants

Metal-free carbon nitride with controlled carbon dopants (ACCN) was synthesized by one-step copolymerization of dicyandiamide (DCD) and ammonium citrate (AC). The obtained ACCN possesses narrower band gap compared to pure graphitic carbon nitride (CN), contributing to broader utilization region of visible light. It exhibits downshifted conduction band and valence band potential with the increased addition of AC. Carbon atoms replace the bridging nitrogen atoms in the framework of ACCN during calcination process, which greatly increase its electrical conductivity and charge separation efficiency. In addition, nitrogen defects and some carbon species linked to the introduced carbon atoms are detected in ACCN. They can also serve as electrons sink to promote the separation of electron-hole pairs. As a consequence, ACCN possesses improved redox ability in the degradation of sulfamethazine (SM2) under visible light. The removal ratio by optimal ACCN achieves 81% in 60 min and its reaction apparent rate constant (0.0277 min−1) is 6.6 times higher than that of CN (0.0042 min−1). Furtherly, the mechanism and reaction process during the photocatalytic degradation are studied specifically. This work provides a facile and green strategy to prepare nonmetal modified CN with boosting photo-redox ability for pollutants treatment.

Cyclobis(7,8‐(para‐quinodimethane)‐4,4′‐triphenylamine) and Its Cationic Species Showing Annulene‐Like Global (Anti)Aromaticity

Abstractπ‐Conjugated macrocycles containing all‐benzenoid rings usually show local aromaticity, but reported herein is the macrocycle CBQT, containing alternating para‐quinodimethane and triphenylamine units displaying annulene‐like anti‐aromaticity at low temperatures as a result of structural rigidity and participation of the bridging nitrogen atoms in π‐conjugation. It was easily synthesized by intermolecular Friedel–Crafts alkylation followed by oxidative dehydrogenation. X‐ray crystallographic structures of CBQT, as well as those of its dication, trication, and tetracation were obtained. The dication and tetracation exhibited global aromaticity and antiaromaticity, respectively, as confirmed by NMR measurements and theoretical calculations. Both the dication and tetracation possess open‐shell singlet ground states, with a small singlet–triplet gap.

Cyclobis(7,8-(para-quinodimethane)-4,4'-triphenylamine) and Its Cationic Species Showing Annulene-Like Global (Anti)Aromaticity.

π-Conjugated macrocycles containing all-benzenoid rings usually show local aromaticity, but reported herein is the macrocycle CBQT, containing alternating para-quinodimethane and triphenylamine units displaying annulene-like anti-aromaticity at low temperatures as a result of structural rigidity and participation of the bridging nitrogen atoms in π-conjugation. It was easily synthesized by intermolecular Friedel-Crafts alkylation followed by oxidative dehydrogenation. X-ray crystallographic structures of CBQT, as well as those of its dication, trication, and tetracation were obtained. The dication and tetracation exhibited global aromaticity and antiaromaticity, respectively, as confirmed by NMR measurements and theoretical calculations. Both the dication and tetracation possess open-shell singlet ground states, with a small singlet-triplet gap.

Low-dimensional compounds containing cyanido groups. Part XXXIV. Structure, spectral and magnetic properties of the first complex with pyridylbenzimidazole and nonlinear pseudohalide anion

Abstract From the system CuCl2 – pbi – NaN(CN)2 −, polymeric [CuCl(μ1,5-dca)(pbi)]n·nH2O (1) complex (dca=dicyanamide, pbi=2-(2-pyridyl)benzimidazole) was isolated and characterized by structure analysis, spectral and magnetic measurements. Infrared spectroscopy confirmed the presence of pbi, dca and water molecules in 1. Its solid-state structure is formed by infinite chains running along the b axis. In the chain, the Cu(II) atom is penta-coordinated by two nitrogen atoms of chelate pbi ligand, by two nitrile nitrogen atoms of bridging μ1,5-dca and by chloride ligand which occupies the apical position of tetragonal pyramid around the Cu(II) atom. Asymmetric unit is supplemented by one molecule of solvated water, which along with chlorine atom serves as acceptors in intermolecular hydrogen bonds and along with π–π interactions create a 3D supramolecular structure. Magnetic measurements revealed the presence of a weak ferromagnetic exchange interaction J/kB =0.11 K.

Investigation of the chromatographic regulation properties of benzyl groups attached to bridging nitrogen atoms in a calixtriazine‐bonded stationary phase

Two reversed-phase/anion-exchange mixed-mode stationary phases for high-performance liquid chromatography using calixtriazines as chromatographic ligands were investigated with Tanaka test solutes, monosubstituted benzenes, aromatic positional isomers, and inorganic anions. Calixtriazine as a chromatographic ligand has been reported previously, but the benzylated nitrogen-bridged calixtriazine-bonded silica gel reported in this study is new. The experimental data showed that the calixtriazine platform is a unique chromatographic selector because its multiple active sites are available for different solutes and its chromatographic selectivity could be tuned by introducing substituent on the bridging nitrogen atoms present in the calixtriazine matrix. The synergistic effects of aromatic rings, nitrogen atoms, benzyl groups, and tunable cavity in the host molecule influenced the separation selectivity by multiple retention mechanisms. Such hybrid stationary phases provide more versatility and have great potential in the analysis of complex samples. Moreover, the synthetic protocols presented herein may provide an alternative understanding on macrocyclic host-guest chemistry, leading to new and selective separation media.

Proton Sponge Analogue of the Tröger's Base: A Compound with Remarkable Enantiomeric Stability

AbstractProton sponge analogue of the Tröger's base (4) has been obtained upon treatment of 1‐amino‐4,5‐bis(dimethylamino)naphthalene with paraformaldehyde. It was found that in contrast to classical Tröger's base 1, protonation of 4 occurs, at least thermodynamically, exclusively on peri‐NMe2 groups producing a dication with two chelated [NHN]+ hydrogen bonds. This prevents the protonation of the bridge nitrogen atoms, which is responsible for rather easy racemization of 1. Indeed, two enantiomers of 4 were resolved by chiral chromatography and their much higher stability in acidic media as compared to 1 has been confirmed. Some other properties of base 4 including structure, basicity, dynamic NMR behavior, host‐guest interactions and reactions with electrophiles are also discussed.

Solving the Hydrogen and Lithium Substructure of Poly(triazine imide)/LiCl Using NMR Crystallography

Poly(triazine imide) with incorporated lithium chloride has recently attracted substantial attention due to its photocatalytic activity for water splitting. However, an apparent H/Li disorder prevents the delineation of structure-property relationships, for example, with respect to band-gap tuning. Herein, we show that through a combination of one- and two-dimensional, multinuclear solid-state NMR spectroscopy, chemical modelling, automated electron diffraction tomography, and an analysis based on X-ray pair distribution functions, it is finally possible to resolve the H/Li substructure. In each cavity, one hydrogen atom is bound to a bridging nitrogen atom, while a second one protonates a triazine ring. The two lithium ions within each cavity are positioned between two nitrogen atoms of neighbouring triazine rings. The thereby induced local dipole moments cause slight buckling of the framework and lateral displacements of the Cl- ions at a coherence length below 2 nm. Nevertheless, the average structure conforms to space group P21 21 21 . In this way, we demonstrate that, in particular, the above-mentioned techniques allow for smart interplay in delineating the real structure of PTI/LiCl.

Selective Formylation of Azacalixpyridine Macrocycles and Their Transformation to Molecular Semicages.

The aromatic electrophilic formylation reaction of azacalix[2]arene[2]pyridine and azacalix[4]pyridine were systematically studied. By simply controlling the ratio of reactants and the reaction temperature, the Vilsmeier-Haack reaction selectively afforded mono-, di-, and tetra-formylated azacalix[2]arene[2]pyridines and azacalix[4]pyridines. The preferential and selective functionalization reactions of macrocycles were discussed in terms of their conformational structure and conjugation effect between aromatic subunits and bridging nitrogen atoms. All resulting functionalized azacalix[2]arene[2]pyridines and azacalix[4]pyridines adopted a 1,3-alternate conformation both in the crystalline state and in solution. Taking advantage of the close proximity of aldehyde groups in 1,3-alternate di- and tetra-formylated azacalixpyridine macrocycles, the McMurry reductive coupling reaction of carbonyls was accomplished to yield unique semicage molecules.