Subsequent Coordination Research Articles

Enhanced removal of azo dye using modified PAN nanofibrous membrane Fe complexes with adsorption/visible-driven photocatalysis bifunctional roles

A series of polyacrylonitrile (PAN) nanofibrous membrane Fe complexes as the Fenton heterogeneous catalysts were fabricated through surface modification with different ratio of hydrazine hydrate (HH) and hydroxylamine (HA) and subsequent coordination with Fe3+ ions for the synergistic removal of a typical azo dye, Reactive Red 195 (RR 195) via adsorption and visible-driven photocatalytic oxidation. Effect of molar ratio of HH and HA on surface structure characteristics of the resulting complexes were examined. Their adsorptive or photocatalytic activity was also compared by changing molar ratio of HH and HA. The results indicated that three PAN nanofibrous membrane Fe complexes prepared with simultaneous modification of HA and HH exhibited much higher adsorption and visible photocatalytic activities than the complex modified solely with HA or HH due to their distinctive surface structures containing more active sites. Their adsorption and visible photocatalytic kinetics of RR 195 followed pseudo-second-order model equation. Their high photocatalytic rate constant and large amount of dye adsorption were regarded as the main reasons for better dye removal efficiency and durability in cyclic reuse by means of the synergistic adsorption-photocatalysis process.

CuI heterogenized on thiosemicarbazide modified‐multi walled carbon nanotubes (thiosemicarbazide‐MWCNTs‐CuI): Novel heterogeneous and reusable nanocatalyst in the C‐N Ullmann coupling reactions

Herein we described the synthesis of novel thiosemicarbazide‐MWCNTs‐CuI nanocatalyst by covalent grafting of thiosemicarbazide on carbon nanotubes surface and subsequent coordination with CuI catalyst. The formation of nanocatalyst was analyzed by Raman spectroscopy, energy dispersive spectroscopy (EDS), wavelength‐dispersive X‐ray spectroscopy (WDX) and ICP analysis. The morphology of the nanocatalyst was characterized using scanning and transmission electron microscopes (SEM and TEM). Additionally, the (thiosemicarbazide‐MWCNTs‐CuI) nanocatalyst was successfully employed in the N‐arylation of indole, amines and imidazoles through intermolecular C(aryl)‐N bond formation from the corresponding aryl halides (Ar–I, Ar–Br, Ar–Cl) with amines through Ullmann‐type coupling reactions. Interestingly, the novel catalyst could be recovered and recycled five times.

Neutral interlocked assemblies from anionic pseudorotaxanes coordinated to Sn(IV) and Cu(I) metallic centers

Anionic [2]pseudorotaxanes have been prepared by threading an axle consisting of two dithiophosphonate donor groups attached to a 1,4,5,8-naphthalenediimide (NDI) core through the cavity of the bis-1,5-(dinaphtho)-38-crown-10 ether (15DN38C10). The subsequent coordination of these interlocked, negatively charged species to R3SnCl (R=Me, Ph) and (Ph3P)2CuNO3 yields neutral (pseudo)rotaxanes of the general formula NDI[(CH2CH2O)n(An)PS2“M”]2⊂15DN38C10 (n=1, 2; An=anisole; “M”=R3Sn or (Ph3P)2Cu). Solution and solid state studies of the rotaxanation process show that there are two factors influencing the interaction between the axles and the wheel: the size of the stopper and the length of the side-arms of the axles. When the axle termini are bulky enough to prevent threading, the length of the side-arms has little influence over the self-assembly process. In contrast, when the size of the stopper does not preclude the threading of the axle through the cavity of the crown, the length of the side-arms is the determining factor in the rotaxanation process. These results presented here provide an alternative method for the synthesis of counter-ion free interlocked species, based on anionic axles with donor capabilities that would produce a neutral interlocked architecture upon threading and coordination to cationic metal-containing centers.

Regulation of plasma cell differentiation, migration and class-switch by c-Myb and T-bet

Abstract Humoral responses are tailored to respond most effectively to the invading pathogen. To achieve this, long lasting, protective antibodies of an affinity and isotype appropriate for the immunising antigen or infecting pathogen are produced mainly within germinal centres (GC). Here, we detail the critical, interdependent roles of the transcription factors c-Myb and T-bet in regulating GC egress and plasma cell differentiation. Deletion of c-Myb in mature B cells led to aberrant up-regulation of plasma cell transcription factors within the GC. Indeed, a subset of cycling cells within the GC secreted antibody and were CD138+ Blimp-1-GFP+. T-bet-regulated genes were also modulated, resulting in significantly elevated serum IgG2c and CXCR3 expression on plasma cells despite a Th2-biased immunization with NP-KLH in alum. These aberrant plasma cells within the GC were no longer evident upon deletion of T-bet in c-Myb-deficient mice. Surprisingly, this interplay between transcription factor networks also occurred during a response to influenza infection, in which T-bet expression is a normal component of B cell responses in wild-type mice. Chromatin accessibility studies of the T-bet promoter revealed that wild-type GC B cells from flu-infected mice had an increase in accessibility in comparison to naïve B cells, as expected. In line with the cellular data, however, there was an even further increase in chromatin accessibility in c-Myb-deficient GC B cells. Therefore, c-Myb establishes a transcription factor network during an immune response that can modulate the transcriptional network of T-bet and subsequent coordination of GC egress with plasma cell differentiation.

Synthesis of Iron-Phosphine Complexes Containing Sulfur Linking Groups for Coordination to PbS Nanoparticles

The synthesis of a bidentate phosphine, 1,2-bis(bis(4-methylthio)phenyl)phosphino)ethane (DpPSMePE), for coordination to both iron (through the phosphines) and subsequent outer-sphere coordination to PdS nanoparticles (through distal –SMe moieties) is presented. Coordination to iron yielded two distinct coordination complexes: trans-FeCl2(DpPSMePE)2 and (μ-DpPSMePE-κP:κP′)2(FeCl2)2. The trans-FeCl2(DpPSMePE)2 complex is high-spin, (μeff = 4.55 BM) with four unpaired electrons. The attempted formation of a hydride complex and its coordination to PbS nanoparticles are discussed.

Mechanism of the Iron(II)-Catalyzed Hydrosilylation of Ketones: Activation of Iron Carboxylate Precatalysts and Reaction Pathways of the Active Catalyst.

A detailed mechanistic study of the catalytic hydrosilylation of ketones with the highly active and enantioselective iron(II) boxmi complexes as catalysts (up to >99% ee) was carried out to elucidate the pathways for precatalyst activation and the mechanism for the iron-catalyzed hydrosilylation. Carboxylate precatalysts were found to be activated by reduction of the carboxylate ligand to the corresponding alkoxide followed by entering the catalytic cycle for the iron-catalyzed hydrosilylation. An Eyring-type analysis of the temperature dependence of the enantiomeric ratio established a linear relationship of ln(S/R) and T(-1), indicating a single selectivity-determining step over the whole temperature range from -40 to +65 °C (ΔΔG(‡)sel,233K = 9 ± 1 kJ/mol). The rate law as well as activation parameters for the rate-determining step were derived and complemented by a Hammett analysis, radical clock experiments, kinetic isotope effect (KIE) measurements (kH/kD = 3.0 ± 0.2), the isolation of the catalytically active alkoxide intermediate, and DFT-modeling of the whole reaction sequence. The proposed reaction mechanism is characterized by a rate-determining σ-bond metathesis of an alkoxide complex with the silane, subsequent coordination of the ketone to the iron hydride complex, and insertion of the ketone into the Fe-H bond to regenerate the alkoxide complex.

Cell division of neurons in an oxygen-glucose deprivation model

Event Abstract Back to Event Cell division of neurons in an oxygen-glucose deprivation model Itsuki Ajioka1, 2* and Mio Oshikawa1 1 Tokyo Medical and Dental University (TMDU), Center for Brain Integration Research (CBIR), Japan 2 JST, PRESTO, Japan Although neurons are able to re-enter the cell cycle in pathological situations such as neurodegeneration and stroke, they are tightly protected from cell division and undergo cell death after S phase progression. Neurons become permanently post-mitotic immediately after cell cycle exit during development, however, the mechanism underlying non-dividing feature is mostly unknown. The Retinoblastoma protein family (Rb, p107, p130) plays a central role in preventing cells from entering the S phase. When Rb family expression is lost in neuronal progenitor cells, the subsequent coordination of cell-cycle exit and neuronal differentiation is lost, and neurons can divide in some cases such as retinoblastoma (Ajioka et al., 2007). We recently developed a technique for conditionally inactivating all of the Rb family members in mouse cortical progenitors, either before or immediately after cell-cycle exit, by electroporation with Cre-expressing plasmids containing a ubiquitous pCAG promoter or a neuron-specific pMAP2 promoter (Oshikawa et al., 2013). When the Rb family is inactivated using pCAG-Cre, immature neurons generated from the pCAG-induced Rb-TKO (Rb-/-; p107-/-; p130-/-) progenitors divide. In contrast, the pMAP2-induced Rb-TKO immature neurons enter the S phase, but undergo cell death. Thus, once progenitor daughter cells exit the cell-cycle and initiate neuronal differentiation, they are prevented from undergoing cell division, and maintain mitotic resistance even after acute Rb family inactivation. These findings led us to hypothesize that pathological neurons in the S phase undergo cell death by activating mitotic safeguards. To investigate whether such mitotic safeguard protects pathological neurons in the S phase from undergoing cell division, we used oxygen-glucose deprivation (OGD) model in which post-mitotic cortical neurons undergo cell death after S phase progression and Rb phosphorylation. We demonstrate the cell division of dying OGD neurons in the S phase by inactivating mitotic safeguards. Keywords: Cell Cycle, Cell Division, Phosphorylation, Neuron, retinoblastoma protein family Conference: 14th Meeting of the Asian-Pacific Society for Neurochemistry, Kuala Lumpur, Malaysia, 27 Aug - 30 Aug, 2016. Presentation Type: Poster Presentation Session Topic: 14th Meeting of the Asian-Pacific Society for Neurochemistry Citation: Ajioka I and Oshikawa M (2016). Cell division of neurons in an oxygen-glucose deprivation model. Conference Abstract: 14th Meeting of the Asian-Pacific Society for Neurochemistry. doi: 10.3389/conf.fncel.2016.36.00182 Copyright: The abstracts in this collection have not been subject to any Frontiers peer review or checks, and are not endorsed by Frontiers. They are made available through the Frontiers publishing platform as a service to conference organizers and presenters. The copyright in the individual abstracts is owned by the author of each abstract or his/her employer unless otherwise stated. Each abstract, as well as the collection of abstracts, are published under a Creative Commons CC-BY 4.0 (attribution) licence (https://creativecommons.org/licenses/by/4.0/) and may thus be reproduced, translated, adapted and be the subject of derivative works provided the authors and Frontiers are attributed. For Frontiers’ terms and conditions please see https://www.frontiersin.org/legal/terms-and-conditions. Received: 04 Aug 2016; Published Online: 11 Aug 2016. * Correspondence: Prof. Itsuki Ajioka, Tokyo Medical and Dental University (TMDU), Center for Brain Integration Research (CBIR), Tokyo, Tokyo, Japan, iajioka.cbir@tmd.ac.jp Login Required This action requires you to be registered with Frontiers and logged in. To register or login click here. Abstract Info Abstract The Authors in Frontiers Itsuki Ajioka Mio Oshikawa Google Itsuki Ajioka Mio Oshikawa Google Scholar Itsuki Ajioka Mio Oshikawa PubMed Itsuki Ajioka Mio Oshikawa Related Article in Frontiers Google Scholar PubMed Abstract Close Back to top Javascript is disabled. Please enable Javascript in your browser settings in order to see all the content on this page.

Specific binding modes of Cu(I) and Ag(I) with neurotoxic domain of the human prion protein

Prion diseases are neurodegenerative disorders associated with a conformational change of the normal cellular isoform of the prion protein (PrPC) to an abnormal scrapie isoform (PrPSc). human prion protein (hPrPC) is able to bind up to six Cu(II) ions. Four of them are distributed in the octarepeat domain, containing four tandem-repetitions of the sequence PHGGGWGQ. Immediately outside the octarepeat domain, in so called PrP amyloidogenic region, two additional and independent Cu(II) binding sites, encompassing His96 and His111 residues, respectively, are present. Considering the potential involvement of PrP in cellular redox homeostasis, investigations on Cu(I)–PrP interaction might be also biologically relevant. Interestingly, the amyloidogenic fragment of PrP contains a –M(X)nM– motif, known to act as Cu(I) binding site in different proteins. In order to shed more light on this issue, copper(I) and silver(I) interactions with model peptides derived from that region were analyzed. The results of our studies reveal that both metal ions are anchored to two thioether sulfurs of Met109 and Met112, respectively. Subsequent metal interaction and coordination to His96 and His111 imidazoles are primarily found for Cu(I) at physiological pH. Metal binding was also investigated in the presence of negatively charged micelles formed by the anionic surfactant, sodium dodecyl sulfate (SDS). Our results strongly support that metal binding mode strongly depends on the protein backbone structure. In particular we show that α-helix structuring of the amyloid PrP domain influences both the metal coordination sphere and the binding affinity.

Lost in the Rhythm: Effects of Rhythm on Subsequent Interpersonal Coordination.

Music is a natural human expression present in all cultures, but the functions it serves are still debated. Previous research indicates that rhythm, an essential feature of music, can enhance coordination of movement and increase social bonding. However, the prolonged effects of rhythm have not yet been investigated. In this study, pairs of participants were exposed to one of three kinds of auditory stimuli (rhythmic, arrhythmic, or white-noise) and subsequently engaged in five trials of a joint-action task demanding interpersonal coordination. We show that when compared with the other two stimuli, exposure to the rhythmic beat reduced the practice effect in task performance. Analysis of the behavioral data suggests that this reduction results from more temporally coupled motor movements over successive trials and that shared exposure to rhythm facilitates interpersonal motor coupling, which in this context serves to impede the attainment of necessary dynamic coordination. We propose that rhythm has the potential to enhance interpersonal motor coupling, which might serve as a mechanism behind its facilitation of positive social attitudes.

Alkylation of Asphaltenes Using a FeCl3Catalyst

Friedel–Crafts alkylation as a strategy to convert asphaltenes to maltenes was investigated. It was postulated that conversion of polar hydroxyl groups in the asphaltenes would make the product more soluble in light hydrocarbons. Reactions were performed with oilsands bitumen-derived materials using FeCl3 as a catalyst and o-xylene and methanol, separately. Only the reaction of o-xylene with asphaltenes was mildly beneficial; it resulted in 6% conversion of asphaltenes to maltenes and an increase of 9% in straight-run distillate and vacuum gas oil. The reactions of o-xylene with maltenes and bitumen were detrimental, as was all alkylation reactions with methanol. To better understand the nature of the conversion, the reactions were repeated with model compounds. With 2-naphthol, it was found that dimerization of 2-naphthol to produce (1,1′-binaphthalene)-2,2′-diol (BINOL) and the subsequent coordination with iron were the two dominant reactions. The adverse consequences of FeCl3-catalyzed conversion could be explained by such intermolecular addition reactions. The reaction of 2-naphthol with methanol and FeCl3 also caused some chlorination of the product. The possibility that FeCl3 as a catalyst affected ethers was explored by performing the reaction with dibenzyl ether as feed. It was found that the ether bonds were cleaved. In the presence of o-xylene, ether cleavage was followed by C-alkylation. The increase in maltenes after the reaction of o-xylene with asphaltenes was better explained by C-alkylation following ether cleavage than the reaction between o-xylene and the hydroxyl groups in the asphaltenes. The reaction of dibenzyl ether with methanol produced benzaldehyde, rearrangement products, and heavy gums.

Efficient Self-Assembly of Di-, Tri-, Tetra-, and Hexavalent Hosts with Predefined Geometries for the Investigation of Multivalency.

Coordination-driven self-assembly of differently shaped di- to hexavalent crown-ether host molecules is described. A series of [21]crown-7- and [24]crown-8-substituted bipyridine and terpyridine ligands was synthetized in a "toolbox" approach. Subsequent coordination to 3d transition metal and ruthenium(II) ions provides an easy and fast access to host assemblies with variable valency and pre-defined orientations of the crown-ether moieties. Preliminary isothermal calorimetry (ITC) titrations provided promising results, which indicated the host complexes under study to be suitable for the future investigation of multivalent and cooperative binding. The hosts described herein will also be suitable for the construction of various multiply threaded mechanically interlocked molecules.

Ensemble Coordination Approach in Multi-AGV Systems Applied to Industrial Warehouses

This paper deals with a holistic approach to coordinate a fleet of automated guided vehicles (AGVs) in an industrial environment. We propose an ensemble approach based on a two layer control architecture and on an automatic algorithm for the definition of the roadmap. The roadmap is built by considering the path planning algorithm implemented on the hierarchical architecture and vice versa. In this way, we want to manage the coordination of the whole system in order to increase the flexibility and the global efficiency. Furthermore, the roadmap is computed in order to maximize the redundancy, the coverage and the connectivity. The architecture is composed of two layers. The low-level represents the roadmap itself. The high-level describes the topological relationship among different areas of the environment. The path planning algorithm works on both these levels and the subsequent coordination among AGVs is obtained exploiting shared resource (i.e., centralized information) and local negotiation (i.e., decentralized coordination). The proposed approach is validated by means of simulations and comparison using real plants.

Growing Tiny Flowers of Organometallic Polymers along Carbon Nanotubes

We developed a facile but efficient method to grow tiny flowers of organometallic polymers along carbon nanotubes (CNTs), allowing the combination of synthesis and threading flowers onto CNTs in one step simultaneously. This afforded a catalog of redox-active tiny flower bundles of organometallic polymers with ultrathin petals. Crystallization of polyethylene end-functionalized with cyanoferrate complex (PE-Fe) along CNTs resulted in tiny flowers threaded onto CNTs. Subsequent coordination polymerization of surface-enriched cyanoferrate complex with Fe3+ afforded the formation of polyethylene/Prussian blue/carbon nanotube (PE-PB/CNT) hybrid flower bundles. The flowers were composed of thin petals of 7 nm in thickness, which consisted of a single PE lamellae sandwiched between two PB nanolayers. The hybrid flower bundles fabricated exhibited enhanced thermal stability and electrochemical activity. The intriguing microstructures along with morphology-related properties of hybrid flower bundles made them use...

Modulation of Framework and Centricity: Cation Size Effect in New Quaternary Selenites, ASc(SeO3)2 (A = Na, K, Rb, and Cs).

Four new stoichiometrically equivalent quaternary scandium selenites, ASc(SeO3)2 (A = Na, K, Rb, and Cs) have been hydrothermally synthesized using A2CO3, Sc(NO3)3·xH2O (or ScO3), and SeO2 as starting materials. All four materials share similar bond networks that are composed of corner-shared distorted ScO6 octahedra and SeO3 trigonal pyramids. However, each material reveals different frameworks and centricities. Detailed structural analysis suggests that the structural variation is attributed to the difference in size and subsequent coordination number for the alkali metal cations. Powder second-harmonic generation (SHG) measurements on noncentrosymmetric (NCS) RbSc(SeO3)2 show that the compound has an SHG efficiency similar to that of (NH4)H2PO4. The observed SHG efficiency is due to the remaining net polarization after cancellation of oppositely aligned moments for SeO3 and ScO6 groups. Thorough characterizations such as spectroscopic, thermal, and elemental analyses for the new materials are presented as are dipole moment and out-of-center distortion calculations.

Novel phenanthroline-diaryldiazadiene ligands with heteroditopic coordination spheres.

1,10-Phenanthroline-5,6-diaryldiazadienes are key structures for the development of novel heterodinuclear photocatalysts and for the construction of extended heterocycles of potential biological use. Herein, the first examples of this compound family are presented together with a wide range of initial reactivity studies. Synthetic strategies are presented to access the two first derivatives of the ligand and to accomplish subsequent metal coordination to the phenanthroline sphere.

Electrochemical preparation of nanostructured lanthanum using lanthanum chloride as a precursor in 1-butyl-3-methylimidazolium dicyanamide ionic liquid.

Nanostructured lanthanum was electrochemically prepared on a platinum (Pt) substrate in the room temperature ionic liquid 1-butyl-3-methylimidazolium dicyanamide (BMI-DCA) containing anhydrous LaCl3 at 333 K. The electrochemical reduction behavior of La(iii) was investigated using cyclic voltammetry and chronoamperometry techniques. Cyclic voltammogram revealed that the reduction of La(iii) in BMI-DCA involved an irreversible process controlled by diffusion. Chronoamperometric transient analysis confirmed the diffusion controlled electrodeposition process with the diffusion coefficient of La(iii) species in the range of 10(-10) cm(2) s(-1). The strong complexing capability of DCA(-) anions facilitated the displacement of chloride ligands and induced the solubility of LaCl3. The subsequent coordination of La(iii) and DCA(-) anions forming [La(DCA)4](-) complex anions was monitored by designing amperometric titration experiments. Potentiostatically deposited La-deposits with different nanostructures were characterized by SEM, XRD and XPS analyses. The electrodeposition potential was found to play an important role in controlling the nucleation and growth kinetics of the nanocrystal during the electrodeposition process. Depending on the deposition potential, metallic lanthanum with either nanoparticles or nanoporous structures was obtained.

Rhodium(I)-N-Heterocyclic Carbene Catalyst for Selective Coupling ofN-Vinylpyrazoles with Alkynes via C–H Activation

The complex [Rh(μ-Cl)(IPr)(η2-coe)]2 {IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-carbene, coe = cis-cyclooctene} efficiently catalyzes the coupling of alkynes and N-vinylpyrazole via C–H activation, leading to Markovnikov-selective butadienylpyrazole derivatives under mild conditions. A straightforward approach to cross-conjugated acyclic trienes is also operative through a one-pot alkyne dimerization-hydrovinylation tandem reaction. The proposed mechanism involves C–H activation of vinylpyrazole directed by nitrogen coordination to the metallic center. Subsequent alkyne coordination, insertion, and reductive elimination steps lead to the coupling products. Several key intermediates participating in the catalytic cycle have been detected and characterized, including a κ-N, η2-C═C coordinated vinylpyrazole complex and a RhIII-hydride-alkenyl species resulting from the C–H activation of the vinylpyrazole

Solution‐ and Solid‐State Luminescent Borate Complexes Based on a Substituted π‐Conjugated 2‐(6′‐Hydroxy‐5′‐benzofuryl) Scaffold

AbstractThis paper describes the synthesis of π‐conjugated fluorophores based either on an anil or a benzoxazole scaffold incorporating a rigid 2‐(6′‐hydroxy‐5′‐benzofuryl) fragment. Their subsequent coordination to a BF2 motif led to highly luminescent BIII complexes called boranils or HBBO borate complexes, respectively. All the new compounds were characterized by NMR spectroscopy, mass spectrometry, and elemental analysis. The study of their optical properties in solution revealed two distinct photophysical behaviors depending on the substitution. Complexes bearing a strong electron‐donating p‐nBu2NC6H4 group displayed a marked internal charge transfer (ICT) leading to a pronounced solvatochromism with λem ranging from 507 to 663 nm and quantum yields of up to 87 %. Alternatively, borate complexes functionalized with p‐tBuC6H4 or p‐OMeC6H4 displayed fluorescence in the visible range that is not influenced by the nature of the solvent. Although the emission of the boranils was quenched in the solid state, HBBO borate complexes displayed intense fluorescence from 489 to 567 nm and quantum yields of up to 23 %. Finally, the excited states of a selection of borate complexes were modeled by using time‐dependent DFT, which allowed calculation of the dipole moments of the dyes in their excited states.

Economic Superpower in an Age of Limits

This paper examines macroeconomic policy coordination between Japan and the United States under the locomotive strategy from 1977 to 1979. Previous studies have described the strategy as a fiasco because of its negative economic impact. In fact, the Japanese government, after two years of stimulus packages, quit trying to be a locomotive bringing other developed countries out of their economic difficulties and the u.s. government admitted it in 1979. On the other hand, as this article shows, bilateral cooperation with the United States under this strategy expanded the roles and burdens of Japan, an emerging economic superpower, in international economic policy coordination. Japan’s efforts to implement the strategy made the u.s. government believe that Tokyo would continue to respond to its request to bear larger international responsibilities, while it also increased awareness of Japan’s global role in Tokyo. These bilateral perceptual changes paved the way for subsequent policy coordination and Japan’s assumption of greater burdens, notably the adoption of large-scale stimulus packages under belt-tightening budgets.

Macrocyclic Salen–Bis-NHC Hybrid Ligands and Their Application to the Synthesis of Enantiopure Bi- and Trimetallic Complexes

Salen and NHC ligands are among the most important ligands for homogeneous catalysis. We have recently reported bimetallic complexes, in which both motifs have been merged for the first time. However, the intermetallic distances, which play a crucial role for cooperative bimetallic catalysis, were probably not appropriate in these first-generation hybrid catalysts. To generate heterobimetallic salen/NHC hybrid complexes with intermetallic distances suitable for cooperative catalysis, chiral macrocyclic hybrid ligands featuring a salen and two linked NHC donor moieties have been prepared in the present study. For the ligand formation, chiral enantiopure diamines as well as chiral enantiopure bisimidazoles were employed, and a matched/mismatched situation was found depending on the configuration of both chirality sources. Regioselective complexation of Zn(II), Ni(II), and Pd(II) by the salen N2O2 coordination sphere was efficiently accomplished. Subsequent coordination of the NHC units was achieved for Ag(I...