Tripodal Ligand Research Articles

Control of the geometry and anisotropy driven by the combination of steric and anion coordination effects in CoII complexes with N6-tripodal ligands: the impact of the size of the ligand on the magnetization relaxation time.

Four mononuclear CoII complexes of formula [Co(L)(SCN)2(CH3OH)0.5(H2O)0.5]·1.5H2O·0.75CH3OH (1), [Co(L1)Cl2]·H2O·2CH3CN (2), [Co(L1)(SCN)2]·1.5H2O·CH3OH (3) and [Co(L1)]ClO4·2CH3OH (4) were prepared from the N6-tripodal Schiff base ligands (S)P[N(Me)NC(H)2-Q]3 (L) and (S)P[N(Me)NC(H)1-ISOQ]3 (L1), where Q and ISOQ represent quinolyl and isoquinolyl moieties, respectively. In 1, the L ligand does not coordinate to the CoII ion in a tripodal manner but using a new N,N,S tridentate mode, which is due to the fact that the N6-tripodal coordination promotes a strong steric hindrance between the quinolyl moieties. However, L1 can coordinate to the CoII ions either in a tripodal manner using CoII salts with poorly coordinating anions to give 4 or in a bisbidentate fashion using CoII salt-containing medium to strongly coordinating anions to afford 2 and 3. In the case of L1, there is no steric hindrance between ISOQ moieties after coordination to the CoII ion. The CoII ion exhibits a distorted octahedral geometry for compounds 1-3, with the anions in cis positions for the former and in trans positions for the two latter compounds. Compound 4 shows an intermediate geometry between an octahedral and trigonal prism but closer to the latter one. DC magnetic properties, HFEPR and FIRMS measurements and ab initio calculations demonstrate that distorted octahedral complexes 1-3 exhibit easy-plane magnetic anisotropy (D > 0), whereas compound 4 shows large easy-axis magnetic anisotropy (D < 0). Comparative analysis of the magneto-structural data underlines the important role that is played not only by the coordination geometry but also the electronic effects in determining the anisotropy of the CoII ions. Compounds 2-3 show a field-induced slow relaxation of magnetization. Despite its large easy-axis magnetic anisotropy, compound 4 does not show significant slow relaxation (SMR) above 2 K under zero applied magnetic fields, but its magnetic dilution with ZnII triggers SMR at zero field. Finally, it is worth remarking that compounds 2-4 show smaller relaxation times than the analogous complexes with the tripodal ligand bearing in its arms pyridine instead of isoquinoline moieties, which is most likely due to the increase of the molecular size in the former one.

ATRP catalysts of tetradentate guanidine ligands - do guanidine donors induce a faster atom transfer?

Tripodal tetradentate N donor ligands stabilise the most active ATRP catalyst systems. Here, we set out to synthesise the new guanidine ligand TMG-4NMe2uns-penp, inspired by p-substituted tris(2-pyridylmethyl)amine (TPMA) ligands. The impact of changing pyridine against guanidine donors was examined through solid state and solution experiments and density functional theory (DFT) calculations. In the solid state, the molecular structures of copper complexes based on the ligands TMG-4NMe2uns-penp, TMG-uns-penp and TMG3tren were discussed concerning the influence of a NMe2 substituent at the pyridines and the guanidine donors. In solution, the TMG-4NMe2uns-penp system was investigated by several methods, including UV/Vis, EPR and NMR spectroscopy indicating similar properties to that of the highly active TPMANMe2 system. The redox potentials were determined and related to the catalytic activity. Besides the expected trends between these and the ligand structures, there is evidence that guanidine donors in tripodal ligand systems lead to a better deactivation and possibly a faster exchange within the ATRP equilibrium than TPMA systems. Supported by DFT calculations, it derives from an easier cleavable Cu-Br bond of the copper(II) deactivator species. The high activity was stated by a controlled initiator for continuous activator regeneration (ICAR) ATRP of styrene.

Multi-phosphine-chelated iron-carbide clusters via redox-promoted ligand exchange on an inert hexa-iron-carbide carbonyl cluster, [Fe6(μ6-C)(μ2-CO)4(CO)12]2.

We report the reactivity, structures and spectroscopic characterization of reactions of phosphine-based ligands (mono-, di- and tri-dentate) with iron-carbide carbonyl clusters. Historically, the archetype of this cluster class, namely [Fe6(μ6-C)(μ2-CO)4(CO)12]2-, can be prepared on a gram-scale but is resistant to simple ligand substitution reactions. This limitation has precluded the relevance of iron-carbide clusters relating to organometallics, catalysis and the nitrogenase active site cluster. Herein, we aimed to derive a simple and reliable method to accomplish CO → L (where L = phosphine or other general ligands) substitution reactions without harsh reagents or multi-step synthetic strategies. Ultimately, our goal was ligand-based chelation of an Fe n (μ n -C) core to achieve more synthetic control over multi-iron-carbide motifs relevant to the nitrogenase active site. We report that the key intermediate is the PSEPT-non-conforming cluster [Fe6(μ6-C)(CO)16] (2: 84 electrons), which can be generated in situ by the outer-sphere oxidation of [Fe6(μ6-C)(CO)16]2- (1: closo, 86 electrons) with 2 equiv. of [Fc]PF6. The reaction of 2 with excess PPh3 generates a singly substituted neutral cluster [Fe5(μ5-C)(CO)14PPh3] (4), similar to the reported reactivity of the substitutionally active cluster [Fe5(μ5-C)(CO)15] with monodentate phosphines (Cooke & Mays, 1990). In contrast, the reaction of 2 with flexible, bidentate phosphines (DPPE and DPPP) generates a wide range of unisolable products. However, the rigid bidentate phosphine bis(diphenylphosphino)benzene (bdpb) disproportionates the cluster into non-ligated Fe3-carbide anions paired with a bdpb-supported Fe(ii) cation, which co-crystallize in [Fe3(μ3-CH)(μ3-CO)(CO)9]2[Fe(MeCN)2(bdpb)2] (6). A successful reaction of 2 with the tripodal ligand Triphos generates the first multi-iron-chelated, authentic carbide cluster of the formula [Fe4(μ4-C)(κ3-Triphos)(CO)10] (9). DFT analysis of the key (oxidized) intermediate 2 suggests that its (μ6-C)Fe6 framework remains fully intact but is distorted into an axially compressed, 'ruffled' octahedron distinct from the parent closo cluster 1. Oxidation of the cluster in non-coordinating solvent allows for the isolation and crystallization of the CO-saturated, intact closo-analogue [Fe6(μ6-C)(CO)17] (3), indicating that the intact (μ6-C)Fe6 motif is retained during initial oxidation with [Fc]PF6. Overall, we demonstrate that redox modulation beneficially 'bends' Wade-Mingo's rules via the generation of electron-starved (non-PSEPT) intermediates, which are the key intermediates in promoting facile CO → L substitution reactions in iron-carbide-carbonyl clusters.

Two‐Electron Redox Reactivity of Thorium Supported by Redox‐Active Tripodal Frameworks

AbstractThe high stability of the + IVoxidation state limits thorium redox reactivity. Here we report the synthesis and the redox reactivity of two Th(IV) complexes supported by the arene‐tethered tris(siloxide) tripodal ligands [(KOSiR2Ar)3‐arene)]. The two‐electron reduction of these Th(IV) complexes generates the doubly reduced [KTh((OSi(OtBu)2Ar)3‐arene)(THF)2] (2OtBu) and [K(2.2.2‐cryptand)][Th((OSiPh2Ar)3‐arene)(THF)2](2Ph‐crypt) where the formal oxidation state of Th is +II. Structural and computational studies indicate that the reduction occurred at the arene anchor of the ligand. The robust tripodal frameworks store in the arene anchor two electrons that become available at the metal center for the two‐electron reduction of a broad range of substrates (N2O, COT, CHT, Ph2N2, Ph3PS and O2) while retaining the ligand framework. This work shows that arene‐tethered tris(siloxide) tripodal ligands allow implementation of two‐electron redox chemistry at the thorium center while retaining the ligand framework unchanged.

Two-Electron Redox Reactivity of Thorium Supported by Redox-Active Tripodal Frameworks.

The high stability of the + IVoxidation state limits thorium redox reactivity. Here we report the synthesis and the redox reactivity of two Th(IV) complexes supported by the arene-tethered tris(siloxide) tripodal ligands [(KOSiR2 Ar)3 -arene)]. The two-electron reduction of these Th(IV) complexes generates the doubly reduced [KTh((OSi(Ot Bu)2 Ar)3 -arene)(THF)2 ] (2OtBu ) and [K(2.2.2-cryptand)][Th((OSiPh2 Ar)3 -arene)(THF)2 ](2Ph -crypt) where the formal oxidation state of Th is +II. Structural and computational studies indicate that the reduction occurred at the arene anchor of the ligand. The robust tripodal frameworks store in the arene anchor two electrons that become available at the metal center for the two-electron reduction of a broad range of substrates (N2 O, COT, CHT, Ph2 N2 , Ph3 PS and O2 ) while retaining the ligand framework. This work shows that arene-tethered tris(siloxide) tripodal ligands allow implementation of two-electron redox chemistry at the thorium center while retaining the ligand framework unchanged.

Self-Repairing Ability of Hybrid Cobalt Hydroxide Nanosheets As Oxygen Evolution Catalysts in Alkaline Electrolytes

Introduction Water electrolysis is a key technology to produce H2 from renewable energy. Because proton exchange membrane water electrolyzers (PEMWE) require noble metals as catalysts, alkaline-type electrolyzers, such as alkaline water electrolyzers (AWE) and anion exchange membrane water electrolysis (AEMWE), have attracted much attention for the use of nonnoble-metal-based catalysts. One of the most important issues of AWE is the degradation of catalysts due to generation of reverse current upon shutdown and power fluctuation. Reverse current hardly generates in AEMWE in principle; however, it possibly generates if an electrolyte is supplied instead of pure water.We have previously reported the self-repairing anode catalysts for AWE [1, 2]. A hybrid cobalt hydroxide nanosheet (denoted as Co-ns, Figure 1a), a Brucite-type cobalt hydroxide modified with tripodal ligands (tris(hydroxymethyl)aminomethane), was dispersed in an alkaline electrolyte. Co-ns is deposited on the anode during the electrolysis at 800 mA/cm2 to form a catalyst layer. After the degradation of the catalyst by potential cycling, Co-ns is deposited to retain the catalytic activity. To develop catalysts with higher activity, durability, and repairing ability, the understanding of the electrochemical deposition of Co-ns is quite important. Here, we demonstrate the mechanism of the electrochemical deposition of Co-ns.ExperimentalCo-ns was synthesized according to our previous report [1]. The Co-ns was dispersed in 1 M KOH electrolyte at varied concentrations of Co-ns. Ni electrodes were used as both working and counter electrodes. Reversible hydrogen electrode (RHE) was used as a reference. Constant current electrolysis at 800 mA/cm2 was applied for 30 min, followed by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) to evaluate the oxygen evolution reaction (OER) activity and the amount of deposited Co. These processes ware repeated for several times to characterize the deposition behaviors. Similar experiments were performed, using Co(OH)2 or CoOOH instead of Co-ns.Results and DiscussionCo-ns was transformed into CoOOH by the decomposition of the tripodal ligand. The deposited amount of Co was evaluated by CV, in which the charge of the cathodic currents at 0.8–1.6 V vs. RHE (denoted as Q c) was proportional to the amount of Co measured by ICP-AES. Figure 1b shows the plots of Q c vs. duration of electrolysis. The amounts of deposited CoOOH depended on the concentration of Co-ns. The deposition rates (slope of the curves) gradually decreased along with the progress of the catalyst deposition. During the electrolysis, the electrode potential decreased because of the increased OER activity due to the catalyst deposition. Assuming that the deposition of CoOOH is a pseudo first-order reaction, its rate constant was calculated by dividing the deposition rate by the concentration of Co-ns. The rate constants are linearly correlated with the electrode potential (Figure 1c); thus, the deposition was confirmed to be an electrochemical process. The present results mean that the electrochemical deposition of CoOOH is accelerated when the electrode potential increases due to the degradation of catalysts. Therefore, the self-repairing process is automatically controlled by the condition of the electrode.The electrochemical deposition proceeds with Co(OH)2, whereas CoOOH hardly deposited at the same conditions, indicating that the oxidation of Co2+ to Co3+ is an essential step of the electrochemical deposition. The electrochemical deposition of Co(OH)2 was stopped after 60 min of electrolysis because of the autooxidation of Co(OH)2 by dissolving O2. It was shown that Co-ns is stable in an electrolyte saturated with O2 probably because the organic modification suppresses the autooxidation. Thus, it is shown that the organic modification of cobalt hydroxide is crucial to retain the self-repairing ability in an electrolyzer.ConclusionIn conclusion, the potential dependence of the rate constant and the essential step of electrochemical deposition of Co-ns were elucidated through systematic studies using Co-ns and related metal hydroxide catalysts. These findings lead to the design of self-repairing electrocatalysts with high activity, long lifetime, and high self-repairing ability using organic functionalization.Acknowledgement This work was supported by the JSPS KAKENHI (grant number 20H02821). Part of this study uses outcomes of the development of fundamental technology for the advancement of water electrolysis hydrogen production in the advancement of hydrogen technologies and utilization projects (grant number JPNP14021) commissioned by the New Energy and Industrial Technology Development Organization (NEDO) in Japan.

Probing the mechanism of the dedicated NO sensor [4Fe-4S] NsrR: the effect of cluster ligand environment

NsrR from Streptomyces coelicolor is a bacterial nitric oxide (NO) sensor/nitrosative stress regulator as its primary function, and has been shown to have differential response at low, mid, and high levels of NO. These must correspond to discrete structural changes at the protein-bound [4Fe-4S] cluster in response to stepwise nitrosylation of the cluster. We have investigated the effect of the monohapto carboxylate ligand in the site differentiated [4Fe-4S] cluster cofactor of the protein NsrR on modulating its reactivity to NO with a focus on indentifying mechanistic intermediates. We have prepared a synthetic model [4Fe-4S] cluster complex with tripodal ligand and one single site differentiated site occupied by either thiolate or carboxylate ligand. We report here the mechanistic details of sequential steps of nitrosylation as observed by ESI MS and IR spectroscopy. Parallel non-denaturing mass spectrometry analyses were performed using site-differentiated variants of NsrR with the native aspartic acid, cysteine, or alanine in the position of the forth ligand to the cluster. A mono-nitrosylated synthetic [4Fe-4S] cluster was observed for the first time in a biologically-relevant thiolate-based coordination environment. Combined synthetic and protein data give unprecedented clarity in the modulation of nitrosylation of a [4Fe-4S] cluster.

From the Glovebox to the Benchtop: Air-Stable High Performance Molybdenum Alkylidyne Catalysts for Alkyne Metathesis.

Molybdenum alkylidynes endowed with tripodal silanolate ligands belong to the most active and selective catalysts for alkyne metathesis known to date. This paper describes a new generation that is distinguished by an unprecedented level of stability and practicality without sacrificing the chemical virtues of their predecessors. Specifically, pyridine adducts of type 16 are easy to make on gram scale, can be routinely weighed and handled in air, and stay intact for many months outside the glovebox. When dissolved in toluene, however, spontaneous dissociation of the stabilizing pyridine ligand releases an active species of excellent performance and functional group tolerance. Specifically, a host of polar and apolar groups, various protic sites, and numerous basic functionalities proved compatible. The catalysts are characterized by crystallographic and spectroscopic means, including 95Mo NMR; their activity and stability are benchmarked in detail, and the enabling properties are illustrated by advanced applications to natural product synthesis. For the favorable overall application profile and ease of handling, complexes of this new series are expected to replace earlier catalyst generations and help encourage a more regular use of alkyne metathesis in general.

Mechanistic Insights into the Appel Reaction Mediated by a Poly-Phosphamide Material as a Heterogeneous Catalyst.

Due to notable thermochemical stability, polyphosphamides are often regarded as flame retardants, while molecular phosphamides can serve as versatile Lewis base to catalyze diverse organic transformations. Being chemically analogous to phosphine oxide, phosphamide can also be considered as a mediator for the phosphine-mediated reaction. Herein, an amorphous polymeric material consisting of phosphamide (-NH-P(O)) in the repeating unit (POP) has been prepared via condensation of tris(2-aminoethyl)amine (TREN) and phenyl phosphinic dichloride (PPDC). The POP is isolated as a metal-free and pure organic material which is made of a strong covalent bond and the phosphamide unit is deployed in the organic framework. The presence of phosphamide in the repeating unit of the isolated amorphous POP material can be confirmed by 31P CPMAS NMR, FTIR, and Raman studies. The core-level N 2p and P 2p X-ray photoelectron spectra are in accordance with the presence of tertiary amine nitrogen attached to carbon and secondary amine nitrogen attached to phosphorus. Elemental analyses have depicted approximately 19.7% of phosphorus content in the material, which is being utilized to study the catalytic Appel reaction with 76% conversion of alcohol to a corresponding halide and TON of 462. Quasi in situ Raman study has identified that amino phosphine formed via in situ reduction of the phosphamide unit of the POP catalyzes the halogenation of primary and secondary alcohols with wide substrate scope and functional group tolerance. Kinetic studies have established a first-order dependence with respect to alcohol, while deuterium labeling experiments emphasize that the deprotonation of alcohol is the rate-limiting step. High thermal stability of the material, scope of easy catalyst recyclability, and a cumulative TON of 1386 have led the POP as an emerging pure organic material to be explored further for other phosphine-mediated organocatalysis.

Synthesis of dynamic polymers by amino-yne click reaction using multifunctional amine

Covalent adaptable networks (CANs) have become sustainable alternatives to traditional thermosetting materials due to their powerful reprocessing and rearrangement capabilities. Therefore, developing and investigating reversible reactions that can be used in the construction of CANs is a popular research topic. Amino-yne click chemistry is known for its green characteristics—it is a catalyst-free and efficient reaction—and is widely applied in the synthesis of bio-organic molecules, but there have been few reports on CANs, especially multifunctional amine-based amino-yne click reactions. In this study, various CANs were synthesized via the amino-yne click reaction using multifunctional amines (diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA)), and they were compared with CANs that were prepared from a primary amine (tris(2-aminoethyl) amine (TREN) and a secondary amine (tris[2-(methylamino)ethyl]amine (TMEN)) under the same conditions. The results showed that H-DETA CANs exhibited the smallest glass transition temperature Tg (15 °C) and Young's modulus (105 MPa) because the crosslinker (DETA) contained a low content of primary amine and secondary amine, but its crosslinking density followed the trend of H-TMEN < H-DETA < H-TREN. In addition, the relaxation time, activation energy, and creep rate results for the CANs followed the same trend as the crosslinking density. With the increase in the secondary amine content of the multifunctional amines, the Tg of the CANs increased from 15 °C to 57 °C, the Young's modulus increased from 105 to 666 MPa, and the crosslinking density increased from 955 to 2690 mol/m3. Notably, the increase in the secondary amine content led to the weaker dynamics of the material, namely, prolonged relaxation time, increased activation energy, and decreased creep rate. This work also verified the dynamic exchange mechanism of the materials by the molecular model reaction and the amine solvent dissolution tests. Finally, hot-pressing experiments demonstrated the good plasticity and recovery ability of prepared CANs. This work provides an elegant path for preparing materials in energy and chemical fields such as coatings and rubber.

Post‐Synthetic Covalent Grafting of Amines to NH2‐MOF for Post‐Combustion Carbon Capture

AbstractHerein, a post‐synthetic modification strategy is used to covalently graft polyamines, including ethylenediamine (ED), diethylenetriamine (DETA), tris(2‐aminoethyl)amine (TAEA), and polyethyleneimine (PEI) to the amino‐ligand inside of a Cr‐MOF, NH2‐Cr‐BDC, for post‐combustion carbon capture applications. X‐ray absorption spectroscopy (XAS), X‐ray photoelectron spectroscopy (XPS), and ion chromatography (IC) reveal that ≈45% of the MOF ligands are grafted with polyamines. Next, assessment of CO2 uptake, CO2/N2 selectivity, isosteric heats of CO2 adsorption, separation performance during humid CO2/N2 (15/85) breakthrough experiments, and cyclability, reveals an enhanced performance for the polyamine‐containing composites and the following performance trend: NH2‐Cr‐BDC&lt;ED&lt;DETA&lt;TAEA&lt;PEI. The best‐performing materials, including the TAEA and PEI‐grafted MOFs, offer CO2 uptakes of 1.0 and 1.55 mmol g−1, respectively, at 0.15 bar and 313 K. Further, these composites also offer a high CO2 capacity after 200 temperature swing adsorption/desorption (TSA) cycles in simulated humid flue gas. Last, after soaking the composites in water, there is no loss of CO2 capacity; on the contrary, when the same MOF is impregnated with polyamines using traditional approaches, there is ≈85% CO2 capacity loss after soaking. Thus, this covalent grafting strategy successfully immobilizes amines in MOF pores preventing leaching and hence can be an effective strategy to extend the adsorbent lifetime.

A [CoSiH2] Silylene Synthon Provides Modular Access to Homo- and Heterobimetallic [Co═Si═M] (M = Co, Fe) Silicide Complexes.

Base-stabilized [BP3iPr](H)2CoSiH2(DMAP) (1, [BP3iPr] = PhB(CH2PiPr2)3-; DMAP = 4-dimethylaminopyridine) is a rare instance of a synthon for the simplest "parent" silylene complex (LM═SiH2). Complex 1 was accessed in high yields via double Si-H bond activation in SiH4 by [BP3iPr]Co(DMAP), and in solution, it undergoes rapid exchange between bound and free DMAP by an associative mechanism (as determined by variable-temperature 1H NMR dynamic studies). The DMAP ligand of 1 is readily displaced by metal-based fragments that bind silicon and cleave the Si-H bonds of the SiH2 moiety to produce bimetallic [Co═Si═M] (M = Co, Fe) molecular silicides. Thus, treatment of 1 with 0.5 equiv of (LCoI)2(μ-N2) (L = a tripodal ligand) resulted in the spontaneous formation of [BP3iPr](H)2Co═Si═Co(H)2L (L = [BP2tBuPz], PhB(CH2PtBu2)2(pyrazolyl)- (3); Tp″, HB(3,5-diisopropylpyrazolyl)3- (4)) with the concomitant release of DMAP. The symmetrical silicide [BP3iPr](H)2Co═Si═Co(H)2[BP3iPr] (5) was prepared by treatment of a mixture of 1 and [BP3iPr]Co(DMAP) with 2 equiv of Ph3B, which in this case is required to sequester DMAP as the elimination product Ph3B-DMAP. A heterobimetallic silicide, [BP3iPr](H)2Co═Si═Fe(H)2[SiP3iPr] (7; [SiP3iPr] = PhSi(CH2PiPr2)3), was obtained via in situ KC8 reduction of [SiP3iPr]FeCl and subsequent addition of 1 and Ph3B. These transformations involving a metal-SiH2 derivative demonstrate a fundamentally new type of reactivity for silylene complexes and provide a unique synthetic method for construction of molecular silicide complexes.

Electrocatalysis of the Oxygen Reduction Reaction by Copper Complexes with Tetradentate Tripodal Ligands.

The tetradentate tripodal ligand scaffold is capable of supporting the expected geometries of the copper ion during the oxygen reduction reaction (ORR) catalysis. As such, we probed the reactivity of copper complexes with these types of ligands by electronically and structurally tweaking the tris(pyridin 2-ylmethyl)amine (tmpa) scaffold by progressively replacing the terminal pyridines with carboxylate donors. This work shows that systems with one carboxylato donor (bpg = bis(pyridin-2-ylmethyl)glycine), (bpp = (3-(bis(pyridin-2-ylmethyl)amino)propanoic acid)) are active in electrocatalyzing the homogeneous ORR under circumneutral aqueous conditions. Turnover frequencies in the range from 105 to 106 s-1, on par with that for Cu-tmpa under identical conditions, were obtained. It is noteworthy that the CuII/CuI redox potentials for the Cu-bpg, Cu-bpp, and Cu-tmpa systems in phosphate-buffered water (pH 7, under Ar) are similar at -0.409, -0.375, and -0.401 V vs Ag/AgCl, respectively. This is rationalized by the influence of the Lewis acidity of the copper ions on the water coligand. Corroborating this are pKa values for [Cu(tmpa)(H2O)]2+, Cu(bpg)(H2O)]+, and [Cu(bpp)(H2O)]+ of 6.6, 8.8, and 10.2, respectively. Thus, the overall charge of the solution species for all three complexes will be +1 at pH 7 and this will be an important determinant for the redox potentials and, in turn, the catalytic overpotentials, which are also similar. A cis carboxylato donor offers H-bonding possibilities for exogenous resting state water and intermediate hydroperoxo coligands. This is reflected by the higher pKa values for Cu-bpp and Cu-bpg compared with that for Cu-tmpa, with the Cu-bpp system furnishing the least strained H-bonding.

The Synthesis, Crystal Structure, and Magnetic Properties of Mono-Scorpionate Eu(III) Complexes

Three Eu3+ complexes containing a neutral tripodal ligand possessing a predictable coordination mode have been obtained and studied. The trispyrazolylmethane complexes have an aqua ligand in the coordination sphere, forming both the mononuclear species [Eu(HCPz3)H2O(NO3)3] and the dimer [Eu(HCPz3)H2O(CF3SO3)3]2, having a Chinese lantern structure, whereas the use of the methylated tripod leads to the water-free complex, [Eu(HC(PzMe2)3)(NO3)3]. A qualitative analysis of the magnetic susceptibility of polycrystalline samples demonstrated that the magnetic properties can be described using a simple Van Vleck formula with spin–orbit coupling parameter (λ = 383 ÷ 406 cm−1) close to the values for free Eu3+ ions. The stereochemical analysis of the coordination environment of [Ln(HC(PzMe2)3)(NO3)3] has shown that these complexes can be used as diamagnetic model systems to obtain information on the crystal field effects in the paramagnetic monoradical complexes, [LnRad(NO3)3], since both types of compounds have the same type of coordination polyhedron (symmetry point group D3h) and very close Ln–donor atom distances.

Self-Photosensitizing Dinuclear Ruthenium Catalyst for CO2 Reduction to CO.

The promise of artificial photosynthesis to solve environmental and energy issues such as global warming and the depletion of fossil fuels has inspired intensive research into photocatalytic systems for CO2 reduction to produce value-added chemicals such as CO and CH3OH. Among the photocatalytic systems for CO2 reduction, self-photosensitizing catalysts, bearing the functions of both photosensitization and catalysis, have attracted considerable attention recently, as such catalysts do not depend on the efficiency of electron transfer from the photosensitizer to the catalyst. Here, we have synthesized and characterized a dinuclear RuII complex bearing two molecules of a tripodal hexadentate ligand as chelating and linking ligands by X-ray crystallography to establish the structure explicitly and have used various spectroscopic and electrochemical methods to elucidate the photoredox characteristics. The dinuclear complex has been revealed to act as a self-photosensitizing catalyst, which acts not only as a photosensitizer but also as a catalyst for CO2 reduction. The dinuclear RuII complex is highly durable and performs efficient and selective CO2 reduction to produce CO with a turnover number of 2400 for 26 h. The quantum yield of the CO formation is also very high─19.7%─and the catalysis is efficient, even at a low concentration (∼1.5%) of CO2.

Anti-Proliferation and DNA Cleavage Activities of Copper(II) Complexes of N3O Tripodal Polyamine Ligands

Four ligands based on the 2-tert-butyl-4-X-6-{Bis[(6-methoxy-pyridin-2-ylmethyl)-amino]-methyl}-phenol unit are synthesized: X = CHO (HLCHO), putrescine-pyrene (HLpyr), putrescine (HLamine), and 2-tert-butyl-4-putrescine-6-{Bis[(6-methoxy-pyridin-2-ylmethyl)-amino]-methyl}-phenol (H2Lbis). Complexes 1, 2, 3, and 4 are formed upon chelation to copper(II). The crystal structure of complex 1 shows a square pyramidal copper center with a very weakly bound methoxypridine moiety in the apical position. The pKa of the phenol moiety is determined spectrophotometrically at 2.82–4.39. All the complexes show a metal-centered reduction in their CV at Epc,red = −0.45 to −0.5 V vs. SCE. The copper complexes are efficient nucleases towards the ϕX174 DNA plasmid in the presence of ascorbate. The corresponding IC50 value reaches 7 μM for 2, with a nuclease activity that follows the trend: 2 &gt; 3 &gt; 1. Strand scission is promoted by the hydroxyl radical. The cytotoxicity is evaluated on bladder cancer cell lines sensitive (RT112) or resistant to cisplatin (RT112 CP). The IC50 of the most active complexes (2 and 4) is 1.2 and 1.0 μM, respectively, for the RT112 CP line, which is much lower than cisplatin (23.8 μM).

Synthesis and VCD Spectroscopic Characterization of a Series of Azacryptands from a Chiral Valine-Based Derivative of Tris(2-aminoethyl)amine (TREN).

Utilizing experimental and computational vibrational circular dichroism (VCD) spectroscopy, we explored the conformational preferences of a series of chiral C3 -symmetric octaazacryptands with tris(2-aminoethyl)-amine head groups derived from valine. While the spectra of the smallest azacryptand with p-phenyl linkers and its elongated derivative with p-biphenyls linker were found to match well with the computed spectra, the computed conformational preferences of the m-biphenyl-based azacryptand did not seem to reflect the conformations dominating in chloroform solution. A detailed analysis revealed that structural changes resulting in a collapsed cage structure gave a notably better match with the experiment. It could subsequently be concluded from the VCD analysis, that the octaazacryptands prefer a collapsed structure, which is not predicted by density functional theory (DFT) calculations as the global minimum structures. These findings are expected to have consequences also for future studies on inclusion complexes of such azacryptands.

Mutual induced‐fit controlled signal amplification of hydrogen‐bonded capsule formation

AbstractMutual induced‐fit is well known process in biological system and playing crucial role in enzymatic catalysis, peptide‐bond synthesis, protein synthesis, etc…, proceeds by mutual interactions of two or more than two components. However, in an artificial system, to mimic such process is challenging, especially by purely organic components. In this report, we have shown importance of mutual induced‐fit in signal amplification of hydrogen‐bonded capsule formation. Two different types of highly flexible ligands (one N‐bridged and another triazine‐bridged) are used. N‐bridged tripodal ligand acting as clip over the adduct obtained from triazine‐bridged ligand, bringing the resultant adduct in the cone‐shape conformation. The resulting cone‐shape conformation undergo solvent polarity dependent hydrogen‐bonded capsule formation as a sole product. In absence of N‐bridged tripodal ligand, only 50% capsule formation is observed through 1H NMR at 100 mM concentration. However, in the presence of N‐bridged tripodal ligand, organic components undergo mutual interactions to opt the cone‐shape conformation and 100% capsule is formed (independent of concentration). The complete process is characterized by IR‐spectra, 1H and 13C NMR spectra, concentration dependent 1H NMR titration spectra, 1H‐1H COSY, 1H‐1H NOESY, DOSY NMR, high resolution ESI mass spectra, and also by energy‐minimized structure.

The Effect of Mixed Ligands on the Polymerization Rate of SET-LRP in Aqueous Solution

Abstract The mixed-ligand effect is investigated in single electron transfer-living radical polymerization (SET-LRP) of OEOMA in aqueous solution for the first time. Mediated by equimolar tris(2-aminoethyl)amine (TREN) and tris(dimethylaminoethyl)amine (Me6-TREN), SET-LRP exhibits the highest polymerization rate while maintaining living characteristics. The higher concentration of self-assembled micellar particles formed by amphiphilic initiator and monomer in aqueous solution under the influence of mixed ligands may be considered as one of factors for the mixed-ligand effect.

Epoxy SQ-based amine functionalized superhydrophilic hybrid network for Ag+ adsorption and catalytic degradation of Rhodamine B

Most epoxy substituted silsesquioxane (SQ)-based materials are hydrophobic, it is of great interest to develop hydrophilic epoxy SQ-based materials for special applications. In this work, epoxy functionalized SQ with T10 (G-SQ) as main product was obtained by the hydrolytic condensation of 3-(glycidoxypropyl)trimethoxysilane; then the hybrid network of G-SQ-TAEA was produced by the amine-epoxy click reaction of G-SQ with tris(2-aminoethyl)amine (TAEA). The introduction of hydroxyl groups and the amine groups by the amine-epoxy click reaction greatly enhances the hydrophilicity of the hybrid network and facilitates the dispersion of G-SQ-TAEA in water. Interestingly, G-SQ-TAEA can adsorb Ag+ ions with a saturation capacity of 86.4 mg/g and the Ag-loaded G-SQ-TAEA (G-SQ-TAEA-Ag) can efficiently catalyze degradation of Rhodamine B (RhB) to colourless. This work offers a new strategy for removing contamination in water.