Pyridine Ligands Research Articles

Mechanisms for the Spin-State Switching of Strapped Ni-Porphyrin Complexes Deposited on Metal Surfaces: Insights from Quantum Chemical Calculations.

The incorporation of molecular switches on nanodevices requires both the intactness of the molecule once deposited on a substrate and the persistence of the reversible switching feature. Recently, the reversible spin-switching of strapped Ni(II)-porphyrin complexes deposited on Ag(111) surface is demonstrated with low-temperature scanning tunneling microscopy (STM). The spin transition is accompanied by the coordination change of the metal center, a phenomenon denominated in coordination-induced spin-state switching (CISSS). In this contribution, the spin switching of the deposited strapped Ni-porphyrin molecules using different quantum chemistry approaches is explored. This calculations inform about the geometry and electronic structure of the adsorbed molecules and the origin of the voltage-dependent switching promoted by the STM tip. Two different mechanisms are inspected to elucidate the key role of the tip, mainly the electron injection between the tip and the molecule and the differential stabilization of the two spin states by the applied electric field between the tip and the silver surface. This study puts in evidence the relevance of the pyridine ligand contained in the strap in the transport properties as in the CISSS process itself.

Crystal structure of bis{5-(4-chlorophenyl)-3-[6-(1H-pyrazol-1-yl)pyridin-2-yl]-1H-1,2,4-triazol-1-ido}nickel(II) methanol disolvate

The unit cell of the title compound, [Ni(C16H10ClN6)2]·2CH3OH, consists of a neutral complex and two methanol molecules. In the complex, the two tridentate 2-(3-(4-chlorophenyl)-1H-1,2,4-triazol-5-yl)-6-(1H-pyrazol-1-yl)pyridine ligands coordinate to the central NiII ion through the N atoms of the pyrazole, pyridine and triazole groups, forming a pseudooctahedral coordination sphere. Neighbouring tapered molecules are linked through weak C—H(pz)...π(ph) interactions into monoperiodic chains, which are further linked through weak C—H...N/C interactions into diperiodic layers. The intermolecular contacts were quantified using Hirshfeld surface analysis and two-dimensional fingerprint plots, revealing the relative contributions of the contacts to the crystal packing to be H...H 32.8%, C...H/H...C 27.5%, N...H/H...N 15.1%, and Cl...H/H...Cl 14.0%. The average Ni—N bond distance is 2.095 Å. Energy framework analysis at the HF/3–21 G theory level was performed to quantify the interaction energies in the crystal structure.

In Situ FT-IR Spectroelectrochemistry Reveals Mechanistic Insights into Nitric Oxide Release from Ruthenium(II) Nitrosyl Complexes.

Ruthenium(II) tetraamine nitrosyl complexes with N-heterocyclic ligands are known for their potential as nitric oxide (NO•) donors, capable of releasing NO• through either direct photodissociation or one-electron reduction of the Ru(II)NO+ center. This study delivers a novel insight into the one-electron reduction mechanism for the model complex trans-[RuII(NO)(NH3)4(py)]3+ (RuNOpy, py = pyridine) in phosphate buffer solution (pH 7.4). In situ FT-IR spectroelectrochemistry reveals that the pyridine ligand is readily released upon one-electron reduction of the nitrosyl complex, a finding supported by nuclear magnetic resonance spectroscopy (1H NMR) and electrochemistry coupled to mass spectrometry (EC-MS), which detect free pyridine in solution. However, direct evidence of NO• release from RuNOpy as the primary step following reduction was not observed. Interestingly, FT-IR results indicate that the isomers of the nitrosyl complex, cis-[Ru(NO)(NH3)4(OH)]+ and trans-[Ru(NO)(NH3)4(OH)]+, are formed following reduction and pyridine labilization, initiating an outer-sphere electron transfer process that triggers a chain electron transfer reaction. Finally, nitric oxide is liberated as an end product, arising from the reduction of the hydroxyl isomer complexes cis-[Ru(NO)(NH3)4(OH)]2+ and trans-[Ru(NO)(NH3)4(OH)]2+. This study provides new insights into the reduction mechanism and transformation pathways of ruthenium nitrosyl complexes, contributing to our understanding of their potential as NO• donors.

PnictogenIIIDications Supported by BZIMPY Ligands.

Two homologous series of pnictogen(III) dications, stabilized by 2,6-bis(benzimidazole-2-yl)pyridine ligands have been prepared. Both series contain PnIII-X moieties (Pn = P, As, Sb, Bi; X = Cl or Ph) and have been fully characterized using spectroscopic methods including X-ray crystallography. The Lewis acidity of these compounds has also been probed by computational methods; the results suggest that the dictations are strong Lewis acids, with the PnCl2+ compounds being more acidic than the PnPh2+ compounds, and with Lewis acidity increasing from P to Bi, in both series. The PhP2+-containing compound was also found to be a versatile PIII transfer reagent, leading to new synthetic routes for various PhP-containing compounds. The redox chemistry of all compounds has also been probed using cyclic voltammetry and chemical reductions. In some cases the resulting PnI moieties could be trapped using diazabutadienes.

Deuteration and Tritiation of Pharmaceuticals by Non-Directed Palladium-Catalyzed C-H Activation in Heavy and Super-Heavy Water.

Deuterated and tritiated analogs of drugs are valuable compounds for pharmaceutical and medicinal chemistry. In this work, we present a novel hydrogen isotope exchange reaction of drugs using non-directed homogeneous Pd-catalysis. Aromatic C-H activation is achieved by a commercially available pyridine ligand. Using the most convenient and cheapest deuterium source, D2O, as the only solvent 39 pharmaceuticals were labelled with clean reaction profiles and high deuterium uptakes. Additionally, we describe the first application of non-directed homogeneous Pd-catalysis for H/T exchange on three different pharmaceuticals by using T2O as isotopic source, demonstrating the applicability to the synthesis of radiotracers.

Deuteration and Tritiation of Pharmaceuticals by Non‐Directed Palladium‐Catalyzed C−H Activation in Heavy and Super‐Heavy Water

AbstractDeuterated and tritiated analogs of drugs are valuable compounds for pharmaceutical and medicinal chemistry. In this work, we present a novel hydrogen isotope exchange reaction of drugs using non‐directed homogeneous Pd‐catalysis. Aromatic C−H activation is achieved by a commercially available pyridine ligand. Using the most convenient and cheapest deuterium source, D2O, as the only solvent 39 pharmaceuticals were labelled with clean reaction profiles and high deuterium uptakes. Additionally, we describe the first application of non‐directed homogeneous Pd‐catalysis for H/T exchange on three different pharmaceuticals by using T2O as isotopic source, demonstrating the applicability to the synthesis of radiotracers.

Ancillary Ligand-Promoted Charge Transfer in Bis-indole Pyridine Ligand-Based Nickel Complexes.

There is growing demand for the utilization of first-row transition metal complexes in light-driven processes instead of their conventional noble metal counterparts due to the greater sustainability of first-row transition metal complexes. However, their major drawback is the ultrafast lifetime of the electronic excited states of these first-row transition metal complexes, particularly those of d8 square-planar systems such as Ni(II) complexes, wherein low-lying metal-centered (MC) states provide the deactivation pathway. To increase the excited-state lifetime and broaden their applications, it is important to develop sterically bulky, strong field ligands with low-lying π* orbitals and a highly σ-donating nature to augment the energy of MC states. The current strategy relies on synthetically carbene-based ligands, which are substitutionally cumbersome and act as σ-donors only. In this work, we introduce a bis-indole pyridine (H2BIP) ligand framework, whose dianionic congener (BIP) demonstrates the ability to form stronger covalent bonds with a Ni(II) center compared to neutral donors like carbene and its effect on the complex to produce a less distorted excited-state structure. When conjoined with ancillary ligands such as pyridine or lutidine, the BIP ligand orchestrates the formation of low-energy 3CT states, which decay in ∼40 ps.

Symmetry Breaking in a Triferrous Extended Metal Atom Chain.

Semilocal and random phase approximation (RPA) density functional theory (DFT) and complete active space (CASSCF + NEVPT2) methodologies were applied to investigate a new class of extended metal atom chain (EMAC) complexes. A novel triferrous complex has been synthesized recently that does not utilize the usual 2,2'-dipyridylamine (dpa) ligand framework, which essentially always results in a tetragonal coordination environment and general formula M3(dpa)4X2, where X is an anion. Instead, the triferrous complex utilizes a dianionic, 2,6-bis(trimethylsilylamido)pyridine ligand (L2-) resulting in the formation of trigonal complexes with general formula Fe3L3. To better understand the electronic structure of this complex, calculations were utilized to explore the experimentally isolated Fe3L3, and a smaller theoretical complex, in order to compare and contrast with the traditional dpa-based EMACs. Due to the absence of anionic, axial ligands, the sigma nonbonding orbitals formed from the metal d orbitals are lower in energy than in the dpa complexes, and compete with the pi bonding orbitals for occupation in the Fe3L3 complex. While the idealized geometry of these complexes is D3h, a helical distortion of the ligands and subsequent electronic symmetry breaking due to Jahn-Teller distortions are predicted utilizing both semilocal and RPA DFT methods, ending in a C2 structure that closely matches the reported crystal structure. Predicted Mössbauer isomer shifts and ultraviolet/visible (UV/vis) spectra also agree with the experimental data available in the literature. Magnetic coupling constants also indicate ferromagnetic coupling between nearest neighbor irons. Two-dimensional (2D) potential energy surfaces were calculated for a range of fixed Fe-Fe bond lengths, revealing a flat potential energy surface over a wide range of Fe-Fe bond lengths and verifying the ability of RPA to act as a higher-level check on semilocal DFT results. In order to verify the predicted high-spin ground state, CASSCF + NEVPT2 was applied to selected molecular configurations and confirmed the predictions made by DFT. These calculations shed light on the physical ground state electron configuration of Fe3L3 and correlate this electronic configuration with the available experimental data.

Toughening Healable Supramolecular Double Polymer Networks Based on Hydrogen Bonding and Metal Coordination.

Double polymer networks (DNs) consist of two interpenetrating polymer networks and can offer properties that are not merely a sum of the parts. Here, we report an elastic DN made from two supramolecular polymers (SMPs) that consist of the same poly(n-butyl acrylate) (BA) backbone. The two polymers feature different non-covalent binding motifs, which form dynamic, reversible cross-links. The polymers were prepared by reversible addi-ti-on-frag-mentation chain-transfer polymerization of n-butyl acrylate and either the self-complementary hydrogen-bonding motif 2-ureido-4[1H]pyri-mi-dinone, or the 2,6-bis(1'-methyl-benz--imidazolyl)-pyridine ligand, which forms complexes with metal ions. The supramolecular DN made by these components combines features of the single networks, including high thermal stability and resistance to creep. The DN further exhibits excellent healability and displays a higher extensibility and a higher toughness than its constituents. The mechanical characteristics of the DN can be further enhanced by selectively pre-stretching one of the networks, which is readily possible due to the reversible formation of the supramolecular cross-links and their orthogonal stimuli-responsive-ness.

Synthesis of the double spiked µ5-sulfide pentanuclear clusters using thermic reactions of Ru3-mercaptopyridine complexes

The treatment of [Ru3(CO)10(μ-dppm)] with 6-methyl-2-mercaptopyridine (1) or 5-trifluoromethyl-2-mercaptopyridine (2) in refluxing THF for 10 h results in the formation of μ5 sulfide-capped pentanuclear clusters [Ru5(CO)11(μ-H)(μ5-S){μ-κ2N,C-NC5H3(R)})(μ-κ2P2-dppm)2] (R = CH3, 3a, 3a'; R=CF3, 3b,3b') respectively. These compounds exhibit unique structural features, with a μ5-S capped binding trinuclear and dinuclear fragments. The mercaptopyridine ligands undergo S-C bond scission, forming an orthometalated pyridine ligand coordinated to a Ru-Ru bond with a concomitant μ-hydride ligand formation. The structures also feature two dppm ligands, one in the Ru-Ru, which bears the μ-H, and the other bridging the Ru-Ru bond with the orthometallated pyridine. In solution, linkage isomers were observed; they differ in the coordination position of the orthometallated pyridine bonded to the same Ru-Ru bond. A single-crystal X-ray diffraction study confirmed the molecular structures of compounds 3a and 3b. NMR, IR, and HRMS were also carried out.

Synthesis and Photo/Radiation Chemical Characterization of a New Redox-Stable Pyridine-Triazole Ligand.

Photocatalysis using transition-metal complexes is widely considered the future of effective and affordable clean-air technology. In particular, redox-stable, easily accessible ligands are decisive. Here, we report a straightforward and facile synthesis of a new highly stable 2,6-bis(triazolyl)pyridine ligand, containing a nitrile moiety as a masked anchoring group, using copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) click reaction. The reported structure mimics the binding motif of uneasy to synthesize ligands. Pulse radiolysis under oxidizing and reducing conditions provided evidence for the high stability of the formed radical cation and radical anion 2,6-di(1,2,3-triazol-1-yl)-pyridine compound, thus indicating the feasibility of utilizing this as a ligand for redox active metal complexes and the sensitization of metal-oxide semiconductors (e. g., TiO2 nanoparticles or nanotubes).

Dimethylene-Cyclopropanide Units as Building Blocks for Fluorescence Dyes.

Many organic dyes are fluorescent in solution. In the solid state, however, quenching processes often dominate, hampering material science applications such as light filters, light-emitting devices, or coding tags. We show that the dimethylene-cyclopropanide scaffold can be used to form two structurally different types of chromophores, which feature fluorescence quantum yields up to 0.66 in dimethyl sulfoxide and 0.53 in solids. The increased fluorescence in the solid state for compounds bearing malonate substituents instead of dicyanomethide ones is rationalized by the induced twist between the planes of the cyclopropanide core and a pyridine ligand.

2,6-Bis(pyrazol-1-yl)pyridine cobalt-catalyzed high selective hydroboration of alkenes

A novel series of cobalt (II) catalysts featuring 2,6-bis(pyrazol-1-yl)pyridine ligands have been synthesized for the purpose of achieving high selectivity in hydroboration reactions of alkenes. These catalysts function effectively under mild, solvent-free conditions, demonstrating contrasting selectivities: Markovnikov-type selectivity for vinylarenes and anti-Markovnikov-type selectivity for alkyl alkenes. This dual-selectivity system offers a versatile platform for the controlled hydroboration of a diverse range of alkene substrates.

Synthesis, structure, characterization and one pot catalytic activity of half-sandwich iridium(III) complexes

A series of stable mononuclear half-sandwich iridium(III) complexes of the general formula [(η5-C5Me5)Ir(L)Cl](BPh4) has been synthesized in dry methanol using different imino pyridine ligands (L1–L6) and [(η5-C5Me5)2Ir2(µ-Cl)2Cl2] in a 2:1 molar ratio. All complexes were fully characterized by melting point, CHN analysis, FT-IR, UV–visible, 1H NMR, 13C NMR spectroscopy and mass spectrometry. The structure of complex 3 [(η5-C5Me5)Ir(L3)Cl](BPh4) was determined by single crystal X-ray structure analysis, showing a chelating coordination mode of the imino pyridine L3. One pot organic transformations of aldehyde to amide were carried out by complexes 1–6 in toluene at 110 °C in the presence of hydroxyl amine hydrochloride and sodium bicarbonate. The catalytic activity of complex 3 was found to be excellent, showing high conversion with catalytic turnover frequency up to 500.

Production of Lactic Acid via Catalytic Transfer Dehydrogenation of Glycerol Catalyzed by Base Metal Salt Ferrous Chloride and Its NNN Pincer-Iron Complexes.

NNN-Bis(imino) pyridine-based pincer-Fe(II) complexes with an expected trigonal bipyramidal (TBP) geometry equilibrated to a rearranged ion pair of an octahedral dicationic Fe complex containing two bis(imino)pyridine ligands that are neutralized by a tetrahedral dianionic-[FeCl4]2-. Single-crystal X-ray diffraction (SCXRD), high-resolution mass spectrometry (HRMS), and UV-visible (UV-vis) studies suggested that the equilibrium was dictated by the sterics of the R group on the imine N, with the less-crowded groups tilting the equilibrium to the ion pair and the bulky ones favoring the TBP geometry. Electron paramagnetic resonance (EPR) and Evan's magnetic moment measurements indicated that the complexes were paramagnetic with Fe(II) in a high-spin state. In solution, over a period of 7 days, these Fe(II) complexes oxidized to a mixture of low-spin and high-spin Fe(III) species. These pincer-Fe(II) were found to be highly active toward the transformation of biodiesel waste glycerol to value-added lactic acid (LA). Particularly, (Ph2NNN)FeCl2 (0.1 mol %) gave 91% LA with a 99% selectivity at 140 °C using 1.2 equiv of NaOH. With 0.0001 mol % (Ph2NNN)FeCl2, very high turnovers (74% LA, 98% selectivity, 740 000 turnover number (TON) at 4405 turnovers per hour (TOs/h)) were obtained after 7 days. EPR indicated Fe(III) species to be the active catalyst, a few of which were detected by HRMS. Experiments with Hg are suggestive of the mostly homogeneous molecular nature of the catalyst with a minor contribution from heterogeneous Fe nanoparticles.

Enhanced DNA damage and anti-proliferative activity of a novel ruthenium complex with a chlorambucil-decorated ligand

Triphenylphosphine substitution reactions of [RuCl(PPh3)2(tpm)]Cl, 1, featuring tris(pyrazolyl)methane (tpm) as ligand, with the chlorambucil-decorated pyridine ligand PyCA, 3-aminopyridine (PyNH2) and 4-pyridinemethanol (PyOH) afforded the corresponding pyridine complexes 2–4 in high yields. PyCA was preliminarily obtained via esterification of 4-pyridinemethanol with chlorambucil. The new compounds PyCA and 2–3 were characterized by IR and multinuclear NMR spectroscopy. Additionally, the structure of 3 was ascertained by single crystal X-ray diffraction. The in vitro anti-proliferative activity of 2–4 and PyCA was determined against a panel of cancer cell lines, outlining 2 as the most performing compound. Targeted studies were subsequently undertaken using 2 to elucidate mechanistic aspects, including the assessment of ruthenium cellular uptake, cell cycle arrest, production of reactive oxygen species (ROS), western blotting and DNA damage (comet test). Overall, data highlight that the anticancer activity provided by 2 primarily affects the mitochondria pathway with a potential additional contribution from DNA damage.

Thermally and Photoinduced Spin-Crossover Behavior in Iron(II)-Silver(I) Cyanido-Bridged Coordination Polymers Bearing Acetylpyridine Ligands.

We report two new cyanido-bridged Fe(II)-Ag(I) coordination polymers using different acetylpyridine isomers, {Fe(4acpy)2[Ag(CN)2]2} 1 and {Fe(3acpy)[Ag(CN)2]2} 2 (4acpy = 4-acetylpyridine; 3acpy = 3-acetylpyridine) displaying thermally and photoinduced spin crossover (SCO). In both cases, the acetylpyridine ligand directs the coordination polymer structure and the SCO of the materials. Using 4-acetylpyridine, a two-dimensional (2D) structure is observed in 1 made of layers stacked on each other by silver-ketone interactions leading to a complete SCO and reversible thermally and photoswitching of the magnetic and optical properties. Changing the acetyl group to a 3-position, a completely different structure is obtained for 2. The unexpected coordination of the carbonyl group to the Fe(II) centers induces a three-dimensional (3D) structure, leading to statistical disorder around the Fe(II) with three different coordination spheres, [N6], [N4O2], and [N5O]. This disorder gives rise to an incomplete thermally induced SCO with a poor photoswitchability. These results demonstrate that the choice of the acetyl position on the pyridine dictates the structural characteristics of the compounds with a direct impact on the SCO behavior. Remarkably, this work opens interesting perspectives for the future design of Fe-Ag cyanido coordination polymers with judiciously substituted pyridine ligands to tune the thermally and photoinduced SCO properties.

DGA-grafting pyridine for ultra-selective and prior extraction of 99TcO4− from simulated spent nuclear fuel

Selective and prior extraction of 99TcO4− ahead of uranium and plutonium separation is a beneficial strategy for the modern nuclear fuel cycle. Herein, a novel DGA-grafting pyridine ligand BisDODGA-DAPy (L1) was tailored for the efficient separation of TcO4− from simulated spent nuclear fuel based on the selectivity of pyridine and synergistic effect of diglycolamide (DGA) group. Compared to the ligands BisDOSCA-DAPy (L2) and BisDODGA-MPDA (L3) with similar structure, BisDODGA-DAPy (L1) demonstrated the better separation performance including good extraction efficiency, reusability, and high loading capacity for TcO4− under high acidic medium. The interactions of the ligands with Tc(VII)/Re(VII) have been investigated in detail using FT-IR, 1H NMR titration, UV-Vis spectrophotometric titration, ESI-HRMS and DFT simulations. The extraction mechanism affected by the protonation of ligand was elucidated under different acidity. BisDODGA-DAPy (L1) demonstrated the ultra-selective extraction ability for TcO4− from simulated spent nuclear fuel. The maximum SFTc/U and SFTc/Pu values were up to 1.29 × 104 and 5.08 × 103, respectively. In the presence of 9 × 104-fold excess of NO3−, the extraction of TcO4− was almost unaffected. Moreover, the good radiolytic stability further highlights the promising potential of this ligand for 99Tc separation. DFT calculation revealed the dominant role of DAPy and DODGA in TcO4− extraction, providing the theoretical evidence for BisDODGA-DAPy (L1) to selectively bind TcO4− over NO3−.

Blue Luminescent Boron Complexes Based on N,N‐Type Imidazo[1,5‐a]pyridine Ligand for Mitochondrial Imaging

AbstractWe have synthesized two boron complexes based on N,N‐type bidentate imidazo[1,5‐a]pyridine ligands exhibiting blue emission with good quantum yields in solution. The transient absorption and theoretical studies of the boron complexes indicated the intramolecular charge transfer nature. In addition, one specific complex, 1 a was found to work as a mitochondrial imaging agent.

Two multifunctional Eu-MOFs with dual photochromic and luminous centers for multiple optical switches and anti-counterfeiting properties

In this work, two multifunctional Eu-MOFs with dual photochromic and luminous centers, formulated as Eu3[(ipbp)4·6H2O]·3H2O (1) and Eu[(ipbp)·(p-BDC)·H2O] (2) (ipbp = 1-(3,5-isophthalic acid)-4,4′-bipyridine chloride, p-BDC = terephthalate), were successfully constructed by solvothermal reactions. The carboxylate pyridine ligand gives the two frameworks excellent photochromic properties, while the metal europium endows the two compounds splendid luminous properties. In addition, the application of the two compounds in three kinds of optical switches is further demonstrated. Finally, the two compounds with dynamic multicolor anti-counterfeiting properties were also explored. This work not only proposed bicentric light-emitting and color-changing materials, but also provided a new strategy for studying multiple optical switches and dynamic anti-counterfeiting.