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Modular approach towards functional multimetallic coordination clusters

Polynuclear coordination clusters (PCCs) provide considerable design capabilities towards various functions based on structural non-rigidity and spin state transitions, optical performance, catalytic properties and porosity. The elaboration of new synthetic pathways is fundamental towards advanced switchable and sensing materials, however, the recognition of the structure?property correlations and their optimization is also a key issue. In this context, the current review underlines the role of internal and external functionalization of recognized discrete cluster cores, as the basis for well-designed performance. In particular, we present here the essential update on the recent advances in the overall functionalization of polycyanido-bridged cores (chapter 2). Moreover, we discuss the polymetallic coordination cores constructed with other ligands (short oxido-, hydroxido-, chalcogenido- and other bridges as well as by long multitopic panelling ligands) by indicating the examples of solid-solutions and site selective occupation along the mixed-metal cluster cores (chapter 3), and external decoration of such clusters with ligands, complexes and polynuclear fragments (chapter 4). We also highlight the key properties, indicate the structure?property correlations, and show the power and limitations of the methods used in the presented studies. Finally, we provide the comparison between cyanido-bridged systems and other systems, and indicating possible future research pathways towards the development of PCCs based multicomponent functional systems.

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Development of an Optical Zn2+ Probe Based on a Single Fluorescent Protein

Various fluorescent probes have been developed to reveal the biological functions of intracellular labile Zn2+. Here, we present Green Zinc Probe (GZnP), a novel genetically encoded Zn2+ sensor design based on a single fluorescent protein (single-FP). The GZnP sensor is generated by attaching two zinc fingers (ZF) of the transcription factor Zap1 (ZF1 and ZF2) to the two ends of a circularly permuted green fluorescent protein (cpGFP). Formation of ZF folds induces interaction between the two ZFs, which induces a change in the cpGFP conformation, leading to an increase in fluorescence. A small sensor library is created to include mutations in the ZFs, cpGFP and linkers between ZF and cpGFP to improve signal stability, sensor brightness and dynamic range based on rational protein engineering, and computational design by Rosetta. Using a cell-based library screen, we identify sensor GZnP1, which demonstrates a stable maximum signal, decent brightness (QY = 0.42 at apo state), as well as specific and sensitive response to Zn2+ in HeLa cells (Fmax/Fmin = 2.6, Kd = 58 pM, pH 7.4). The subcellular localizing sensors mito-GZnP1 (in mitochondria matrix) and Lck-GZnP1 (on plasma membrane) display sensitivity to Zn2+ (Fmax/Fmin = 2.2). This sensor design provides freedom to be used in combination with other optical indicators and optogenetic tools for simultaneous imaging and advancing our understanding of cellular Zn2+ function.

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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A novel series of 4,4?-bipyridine- and 1,2-bis(4-pyridyl)ethane-Cu(II) complexes were synthesized using a variety of amine ligands (DPA = di(2-pyridylmethyl)amine, Medpt = 3,3?-diamino-N-methyldipropylamine, Hbpca = bis(2-pyridylcarbonyl)amine, TPA = tris(2-pyridylmethyl)amine) and cyclen = 1,4,7,10-tetraazacyclododecane). Different complexes were obtained including mononuclear [Cu(cyclen)(4,4?-bipy)](ClO4)2 (1), dinuclear {[Cu(mu2-bpca)(4,4?-bipy)(H2O)]ClO4}2 (2), [Cu2(DPA)2(mu2-4,4?-bipy)(ClO4)4)]·H2O (3), [Cu2(cyclen)2(mu2-bpe)](ClO4)4 (4) and [Cu2(TPA)2(mu2-bpe)](ClO4)4 (5) and the 1-D polymer, {[Cu(Medpt)(mu2-4,4?-bipy)](ClO4)2}n (6). In the 1-6 samples, cooling up to 100 K produces only the expected, minor, changes in cell constants given no space group changes. Therefore, data for the 100 K structures are reported only. Single-crystal X-ray crystallography reveals the monodentate coordination of the 4,4?-bipy in 1 and 2, and the bridged nature of the di-pyridyl ligands in the dinuclear complexes 2-5 and in the polymeric complex 6. In this series, structures 3-6 consist of the 4,4?-bipy or bpe bridging the two Cu(II) centers, the coordination by the tri- or the tetra-N donors of the amine, and the ClO4- groups as counter ions in 4-6 complexes. In the complexes 3-6, the Cu···Cu distances across the bridged di-pyridyl ligands were found to be greater than 11 A?. The magnetic properties of complex 3 reveal no evidence for magnetic coupling between the two Cu(II) centers (J = -0.58 cm-1).

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Rhenium(III), (IV) and (V) complexes with 6-hydroxypicolinic acid

The reaction of trans-[ReOBr3(PPh3)2] with 6-hydroxypicolinic acid (H2hpa) in ethanol led to the isolation of the ReIVReIV dimer (mu-O)(mu-hpa)2[Re2Br(OEt)(PPh3)2] (1). Each hpa2- anion acts as a bridging ligand with the coordination of a neutral pyridol oxygen to one rhenium ion, and the coordination of a carboxylate oxygen and a pyridinate nitrogen to the other rhenium ion. By using [ReOCl3(PPh3)2] as precursor in ethanol, two products were isolated, i.e. (mu-Cl)(mu-O)(mu-hpa)[ReIV2Cl2(OEt)(PPh3)2] (2) and [ReIIICl2(Hhpa)(PPh3)2] (3). The complexes cis-[ReOX2(Hhpa)(PPh3)] (X = Br (4); Cl (5)) were the only products formed by the reaction of [ReOX3(PPh3)2] with H2hpa in acetonitrile. The bromide equivalent of 3, i.e. [ReIIIBr2(Hhpa)(PPh3)2] (6), was obtained from the reaction of [ReOBr3(PPh3)2] with H2hpa in 2-propanol. Coordination of Hhpa- in 3-6 occurs through the carboxylate oxygen and neutral pyridyl nitrogen. In addition to the X-ray crystal structures, infra-red, 1H NMR, electrochemical and electronic properties are also reported.

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Structure and spin state of nonheme FeIVO complexes depending on temperature: Predictive insights from DFT calculations and experiments

The spin states (S = 1 and S = 2) of nonheme FeIVO intermediates are believed to play an important role in determining their chemical properties in enzymatic and biomimetic reactions. However, it is almost impossible to investigate the spin state effect of nonheme FeIVO species experimentally, since FeIVO models having the S = 1 and S = 2 spin states at the same time neither exist nor can be synthesized. However, recent synthesis of an FeIVO complex with an S = 1 spin state (triplet), [(Me3NTB)FeIVO]2+ (1), and a structurally similar FeIVO complex but with an S = 2 spin state (quintet), [(TQA)FeIVO]2+ (2), has allowed us to compare their reactivities at 233 K. In the present study, we show that structural variants control the spin-state selectivity and reactivity of nonheme FeIVO complexes. While 1 and 2 were proposed to be in an octahedral geometry based on DFT calculations and spectroscopic characterization done at 4 K, further DFT calculations show that these species may well assume a trigonal bipyramidal structure by losing one coordinated solvent ligand at 233 K. Thus, the present study demonstrates that the structure and spin state of nonheme FeIVO complexes can be different at different temperatures; therefore, the structural and/or spin state information obtained at 4 K should be carefully used at a higher temperature (e.g., 233 K). In addition to 1 and 2, [(TPA)FeIVO]2+ (3) with an S = 1 spin state, whose spin state was determined spectroscopically and theoretically at 233 K, is included in this study to compare the chemical properties of S = 1 and S = 2 FeIVO complexes. The present results add another dimension to the discussion of the reactivites of nonheme FeIVO species, in which the structural preference and spin state of nonheme FeIVO species can vary depending on temperature.

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Kinetic study of catalytic CO2 hydration by metal-substituted biomimetic carbonic anhydrase model complexes

The rapid rise of the CO2 level in the atmosphere has spurred the development of CO2 capture methods such as the use of biomimetic complexes that mimic carbonic anhydrase. In this study, model complexes with tris(2-pyridylmethyl)amine (TPA) were synthesized using various transition metals (Zn2+, Cu2+ and Ni2+) to control the intrinsic proton-donating ability. The pKa of the water coordinated to the metal, which indicates its proton-donating ability, was determined by potentiometric pH titration and found to increase in the order [(TPA)Cu(OH2)]2+ < [(TPA)Ni(OH2)]2+ < [(TPA)Zn(OH2)]2+. The effect of pKa on the CO2 hydration rate was investigated by stopped-flow spectrophotometry. Because the water ligand in [(TPA)Zn(OH2)]2+ had the highest pKa, it would be more difficult to deprotonate it than those coordinated to Cu2+ and Ni2+. It was, therefore, expected that the complex would have the slowest rate for the reaction of the deprotonated water with CO2 to form bicarbonate. However, it was confirmed that [(TPA)Zn(OH2)]2+ had the fastest CO2 hydration rate because the substitution of bicarbonate with water (bicarbonate release) occurred easily. Sometimes chemists are able to propose two or more mechanisms that are consistent with the available data. Related Products of 16858-01-8, If a proposed mechanism predicts the wrong experimental rate law, however, the mechanism must be incorrect.Welcome to check out more blogs about 16858-01-8, in my other articles.

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Frontiers in poly(ionic liquid)s: Syntheses and applications

We review recent works on the synthesis and application of poly(ionic liquid)s (PILs). Novel chemical structures, different synthetic strategies and controllable morphologies are introduced as a supplement to PIL systems already reported. The primary properties determining applications, such as ionic conductivity, aqueous solubility, thermodynamic stability and electrochemical/chemical durability, are discussed. Furthermore, the near-term applications of PILs in multiple fields, such as their use in electrochemical energy materials, stimuli-responsive materials, carbon materials, and antimicrobial materials, in catalysis, in sensors, in absorption and in separation materials, as well as several special-interest applications, are described in detail. We also discuss the limitations of PIL applications, efforts to improve PIL physics, and likely future developments.

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Five-coordinate cobalt(II) complexes of tris(2-pyridylmethyl)amine (TPA): Synthesis, structural and magnetic characterization of a terephthalato-bridged dinuclear cobalt(II) complex

The cobalt(II) complexes [Co(TPA)Cl]ClO4 (1), [Co(TPA)Br]ClO4 (2), [Co(TPA)(H2O)]Cl(ClO4) (3) and [Co2(TPA)2(mu-tp)](ClO4)2 ¡¤ 2H2O (4) (TPA = tris(2-methylpyridyl)amine and tp = terephthalate dianion) were synthesized and structurally characterized by UV-vis and IR spectroscopy. The molecular structures of complexes 1 and 4 were determined by X-ray crystallography and their magnetic properties were measured over the temperature range 2-300 K. The coordination geometry around the central Co(II) in these compounds has a distorted trigonal bipyamidal geometry with four nitrogen atoms from the TPA ligand and the fifth coordination site is occupied by Cl- ion in 1, Br- ion in 2, coordinated oxygen atom from H2O in 3 and by an oxygen atom supplied by the carboxylate group of the bridged terephthalato ligand in 4. The visible spectra of the complexes 1-3 in MeOH show strong distortion toward tetrahedral geometry. For complex 4, analysis of the infrared spectral data for the nu(COO-) stretching frequencies of the tp-carboxalato groups reveals the existence of the bis(monodentate) coordination mode for the bridged tp. X-ray data for 1 and 4 show that the former is mononuclear while the latter is dinuclear. The electronic spectrum of 4 in MeOH is in complete agreement with the assigned X-ray geometry around the Co(II) centers. The magnetic behavior of the mononuclear complex 1 is indicative of a high-spin compound with zero-field splitting. The best fit was obtained with {divides}D{divides} = 7.3 cm-1, g = 2.25. The dinuclear complex 4 exhibits weak antiferromagnetic coupling with a coupling constant J = -0.8 cm-1. The magnetic properties and the structural parameters of 4 are discussed in relation to the other related mu-terephthalato dinuclear Co(II) compounds. The geometry of the coordination sphere around 4 is unique – the CSD compilation listing only one other compound with such a geometry around the dinuclear Co(II) complex and its composition is far different from that in 4. However, they share a common feature of having a weakly antiferromagnetic coupling between Co(II) centers.

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Five-coordinate cobalt(II) complexes of tris(2-pyridylmethyl)amine (TPA): Synthesis, structural and magnetic characterization of a terephthalato-bridged dinuclear cobalt(II) complex

The cobalt(II) complexes [Co(TPA)Cl]ClO4 (1), [Co(TPA)Br]ClO4 (2), [Co(TPA)(H2O)]Cl(ClO4) (3) and [Co2(TPA)2(mu-tp)](ClO4)2 ¡¤ 2H2O (4) (TPA = tris(2-methylpyridyl)amine and tp = terephthalate dianion) were synthesized and structurally characterized by UV-vis and IR spectroscopy. The molecular structures of complexes 1 and 4 were determined by X-ray crystallography and their magnetic properties were measured over the temperature range 2-300 K. The coordination geometry around the central Co(II) in these compounds has a distorted trigonal bipyamidal geometry with four nitrogen atoms from the TPA ligand and the fifth coordination site is occupied by Cl- ion in 1, Br- ion in 2, coordinated oxygen atom from H2O in 3 and by an oxygen atom supplied by the carboxylate group of the bridged terephthalato ligand in 4. The visible spectra of the complexes 1-3 in MeOH show strong distortion toward tetrahedral geometry. For complex 4, analysis of the infrared spectral data for the nu(COO-) stretching frequencies of the tp-carboxalato groups reveals the existence of the bis(monodentate) coordination mode for the bridged tp. X-ray data for 1 and 4 show that the former is mononuclear while the latter is dinuclear. The electronic spectrum of 4 in MeOH is in complete agreement with the assigned X-ray geometry around the Co(II) centers. The magnetic behavior of the mononuclear complex 1 is indicative of a high-spin compound with zero-field splitting. The best fit was obtained with {divides}D{divides} = 7.3 cm-1, g = 2.25. The dinuclear complex 4 exhibits weak antiferromagnetic coupling with a coupling constant J = -0.8 cm-1. The magnetic properties and the structural parameters of 4 are discussed in relation to the other related mu-terephthalato dinuclear Co(II) compounds. The geometry of the coordination sphere around 4 is unique – the CSD compilation listing only one other compound with such a geometry around the dinuclear Co(II) complex and its composition is far different from that in 4. However, they share a common feature of having a weakly antiferromagnetic coupling between Co(II) centers.

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Catalysts function by providing an alternate reaction mechanism that has a lower activation energy than would be found in the absence of the catalyst. In some cases, the catalyzed mechanism may include additional steps.In a article, 16858-01-8, molcular formula is C18H18N4, introducing its new discovery. HPLC of Formula: C18H18N4

Reductive Activation of O2 by Non-Heme Iron(II) Benzilate Complexes of N4 Ligands: Effect of Ligand Topology on the Reactivity of O2-Derived Oxidant

A series of iron(II) benzilate complexes (1-7) with general formula [(L)FeII(benzilate)]+ have been isolated and characterized to study the effect of supporting ligand (L) on the reactivity of metal-based oxidant generated in the reaction with dioxygen. Five tripodal N4 ligands (tris(2-pyridylmethyl)amine (TPA in 1), tris(6-methyl-2-pyridylmethyl)amine (6-Me3-TPA in 2), N1,N1-dimethyl-N2,N2-bis(2-pyridylmethyl)ethane-1,2-diamine (iso-BPMEN in 3), N1,N1-dimethyl-N2,N2-bis(6-methyl-2-pyridylmethyl)ethane-1,2-diamine (6-Me2-iso-BPMEN in 4), and tris(2-benzimidazolylmethyl)amine (TBimA in 7)) along with two linear tetradentate amine ligands (N1,N2-dimethyl-N1,N2-bis(2-pyridylmethyl)ethane-1,2-diamine (BPMEN in 5) and N1,N2-dimethyl-N1,N2-bis(6-methyl-2-pyridylmethyl)ethane-1,2-diamine (6-Me2-BPMEN in 6)) were employed in the study. Single-crystal X-ray structural studies reveal that each of the complex cations of 1-3 and 5 contains a mononuclear six-coordinate iron(II) center coordinated by a monoanionic benzilate, whereas complex 7 contains a mononuclear five-coordinate iron(II) center. Benzilate binds to the iron center in a monodentate fashion via one of the carboxylate oxygens in 1 and 7, but it coordinates in a bidentate chelating mode through carboxylate oxygen and neutral hydroxy oxygen in 2, 3, and 5. All of the iron(II) complexes react with dioxygen to exhibit quantitative decarboxylation of benzilic acid to benzophenone. In the decarboxylation pathway, dioxygen becomes reduced on the iron center and the resulting iron-oxygen oxidant shows versatile reactivity. The oxidants are nucleophilic in nature and oxidize sulfide to sulfoxide and sulfone. Furthermore, complexes 2 and 4-6 react with alkenes to produce cis-diols in moderate yields with the incorporation of both the oxygen atoms of dioxygen. The oxygen atoms of the nucleophilic oxidants do not exchange with water. On the basis of interception studies, nucleophilic iron(II) hydroperoxides are proposed to generate in situ in the reaction pathways. The difference in reactivity of the complexes toward external substrates could be attributed to the geometry of the O2-derived iron-oxygen oxidant. DFT calculations suggest that, among all possible geometries and spin states, high-spin side-on iron(II) hydroperoxides are energetically favorable for the complexes of 6-Me3-TPA, 6-Me2-iso-BPMEN, BPMEN, and 6-Me2-BPMEN ligands, while high spin end-on iron(II) hydroperoxides are favorable for the complexes of TPA, iso-BPMEN, and TBimA ligands.

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Reference£º
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI