Multisite Coordination Research Articles

Cobalt Ditelluride Meets Tellurium Vacancy: An Efficient Catalyst as a Multifunctional Polysulfide Mediator toward Robust Lithium-Sulfur Batteries.

The commercialization of lithium-sulfur batteries (LSBs) faces significant challenges due to persistent issues, such as the shuttle effect of lithium polysulfides (LiPSs) and the slow kinetics of cathodic reactions. To address these limitations, this study proposes a vacancy-engineered cobalt ditelluride catalyst (v-CoTe2) supported on nitrogen-doped carbon as a sulfur host at the cathode. Density functional theory calculations and experimental results indicate that the electron configuration modulation of v-CoTe2 enhances the chemical affinity and catalytic activity toward LiPS. Specifically, v-CoTe2 can strongly interact with PSs through multisite coordination, effectively facilitating the kinetics of the LiPS redox reaction. Furthermore, the introduction of Te vacancies generates a large number of spin-polarized electrons, further enhancing the reaction kinetics of LiPS. As a result, the v-CoTe2@S cathode demonstrates high initial capacity and excellent cyclic stability, maintaining 80.4% capacity after 500 cycles at a high current rate of 3 C. Even under a high sulfur load of 6.7 mg cm-2, a high areal capacity of 6.1 mA h cm-2 is retained after 50 cycles. These findings highlight the significant potential of Te vacancies in CoTe2 as a sulfur host material for LSBs.

Tetranuclear CoII4O4 Cubane Complex: Effective Catalyst Toward Electrochemical Water Oxidation.

The reaction of Co(OAc)2·6H2O with 2,2'-[{(1E,1'E)-pyridine-2,6-diyl-bis(methaneylylidene)bis(azaneylylidene)}diphenol](LH2) a multisite coordination ligand and Et3N in a 1:2:3 stoichiometric ratio forms a tetranuclear complex Co4(L)2(μ-η1:η1-OAc)2(η2-OAc)2]· 1.5 CH3OH· 1.5 CHCl3 (1). Based on X-ray diffraction investigations, complex 1 comprises a distorted Co4O4 cubane core consisting of two completely deprotonated ligands [L]2- and four acetate ligands. Two distinct types of CoII centers exist in the complex, where the Co(2) center has a distorted octahedral geometry; alternatively, Co(1) has a distorted pentagonal-bipyramidal geometry. Analysis of magnetic data in 1 shows predominant antiferromagnetic coupling (J = -2.1 cm-1), while the magnetic anisotropy is the easy-plane type (D1 = 8.8, D2 = 0.76 cm-1). Furthermore, complex 1 demonstrates an electrochemical oxygen evolution reaction (OER) with an overpotential of 325 mV and Tafel slope of 85 mV dec-1, required to attain a current density of 10 mA cm-2 and moderate stability under alkaline conditions (pH = 14). Electrochemical impedance spectroscopy studies reveal that compound 1 has a charge transfer resistance (Rct) of 2.927 Ω, which is comparatively lower than standard Co3O4 (5.242 Ω), indicating rapid charge transfer kinetics between electrode and electrolyte solution that enhances higher catalytic activity toward OER kinetics.

Multistage orbital hybridization induced by multisite exchange interactions in high-entropy perovskites for high oxygen evolution reaction

The oxygen evolution reaction (OER) has garnered considerable attention because of its promising prospects in electrochemical energy conversion applications, but a significant challenge is faced by the insufficient understanding of sluggish OER kinetics. In fact, the intrinsic “acceptance-donation” process of electrons between active sites and reactants is responsible for improving OER activity. Herein, we suggest a multielement hybridization strategy to rematch spin electron occupation and energy splitting in high-entropy perovskites with multiple orbital coordination. In this concept, electronic hopping between t2g and eg orbitals among particular catalytic sites can be obviously enforced due to introducing more favorable energy levels from neighboring metal sites, which can demonstrate multistage orbital hybridization reaction activity. As a result, our proposed multistage-hybridized high-entropy perovskites display an impressive activity of 199.8 mA cm−2 as an overpotential of ∼0.46 V, which is ∼5.3 times that of pristine perovskite. Different from traditional catalyst designs, this study focuses on multistage orbital hybridization and electron exchange interactions through a multisite coordination mechanism to construct a fast reaction pathway. Our findings provide a new strategy for accelerating OER catalytic kinetics.

The one-step synthesis of a novel metal–organic frameworks for efficient and selective removal of Cr(VI) and Pb(II) from wastewater: Kinetics, thermodynamics and adsorption mechanisms

The removal of Cr(VI) and Pb(II) from wastewater is one of the methods to ensure water safety. However, it is still a difficult point to design efficient and selective adsorbent. In this work, Cr(VI) and Pb(II) were removed from water by a new metal–organic frameworks material (MOF-DFSA) with numerous adsorption sites. The max adsorption capacities of MOF-DFSA were 188.12 mg/g for Cr(VI) after 120 min and 349.09 mg/g for Pb(II) within 30 min. MOF-DFSA showed good selectivity and reusability after four cycles. The adsorption of MOF-DFSA was an irreversible process with multi-site coordination, and an active site adsorbed 1.798 Cr (VI) and 0.395 Pb (II). Kinetic fitting showed that the adsorption was chemisorption and surface diffusion was the main limiting step. Thermodynamic showed that Cr(VI) adsorption was enhanced at higher temperatures by spontaneous processes while Pb(II) was weakened. The chelation and electrostatic interaction of the hydroxyl and nitrogen-containing groups of MOF-DFSA with Cr(VI) and Pb(II) is the predominant mechanism, while the reduction of Cr(VI) also play an important role in adsorption. In conclusion, MOF-DFSA was a sorbent that can be used for the removal of Cr(VI) and Pb(II).

Efficient interface modification via multi-site coordination for improved efficiency and stability in organic solar cells

An anthraquinone derivative is developed to modify the SnO2 interface in organic solar cells via the multi-site coordination effect, yielding outstanding photovoltaic performances and device stability.

Multisite Coordination Ligands on Cyclotriphosphazene Core for the Assembly of Metal Clusters and Porous Coordination Polymers

AbstractIn this review, we account the recent advancements on cyclotriphosphazene (N3P3Cl6) based multi‐site coordination ligands for the synthesis of multi‐metallic architectures. In case of N3P3Cl6, Phosphorous centres with two chlorides use to be bonded with nitrogen [−P(Cl2)=N−]3 at alternative positions in six membered ring to provide a robust planar structure to anchor the ligand arms with wide flexibility. Cyclic P−N robust motif is renowned as the potential support for the design of multi‐site ligands originating from phosphorus centres by viable substitution of variable number of ligand units (1 to 6) consist of one or more coordination site(s) via geminal and/or non‐geminal modes. Despite these phosphorus centres are promising to support in ligand structure, occasionally involve in coordination with transition metals as well. Three of alternative nitrogen atoms in this heterocyclic core are supposed to function as Lewis base centres while the electron releasing substituents occurred to tether on phosphorus centres, also when the resultant ring size favours adequate interaction towards the transition metal ions with respect to skeletal flexibility. The ligand modes vary with respect to numbers and orientation of coordination sites, which is imperative to enrich the ligation ability. Moreover, several examples of cyclotriphosphazene core ligands consist of the spacer oxygen atom while tethering with exocyclic ligand units to incorporate more flexibility. In accordance with coordination sites on ligand framework and choice of metal, the skeletal ring nitrogen atom(s) of the cyclotriphosphazene can be involved in coordination with metal ions. Indeed, the coordination of ligands is reported to coordinate with main group, transition and lanthanide metal ions to form variety of metal clusters and porous coordination polymers. Subsequently, the geometry of homo or heterometallic complexes with respect to versatile coordination modes of metallic complexes tends to afford inherent chemical properties for specific application. In terms of exocyclic ligands, the heterocyclic units such as pyridyloxy‐, pyrazolyl‐, pyridylalkylamino‐, bipyridyl‐, 1,10‐phenanthroline, porphyrinato, hydrazide, hydrazone, Schiff's base and spirocyclic amine units attached to cyclotriphosphazene were exploited to form series of metal complexes. Similarly, the variety of metal clusters, polymeric network (1D to 3D) and porous coordination polymers have been reported on basis of cyclic core molecule substituted with ligand units, pyridyloxy‐, multi‐carboxylic, aromatic amines substituted pyridyloxy‐ and imidazole moiety involved to form variety of products.

Bio-behavioural research in a rare disease population: a doctoral student's experience.

Novice researchers who aspire to contribute to the body of knowledge concerning rare diseases face unique challenges in developing and conducting studies. These include unknown effect sizes in previous research, limitations in recruitment and enrolment, and managing data from a multi-site sample. To describe the challenges in researching rare diseases and possible solutions using a doctoral student exemplar from a cross-sectional correlational study of fatigue. The authors discuss the lessons learned from the study, including the challenges in recruitment, communication, collecting biological data and managing data in general. They posit possible solutions, including improving multi-site coordination, feasible methods for exploring sleep and stress, and measures to prevent equipment and data loss. Rare populations, such as young survivors of childhood brain tumours, deserve a voice in building the body of knowledge needed for more precise, personalised healthcare. It is possible with foresight for the novice researcher to make such a contribution. Improved knowledge and assessment of symptoms during childhood will improve the detection of health risk factors and enable earlier intervention.

Heterometallic 3d-4f Complexes as Single-Molecule Magnets.

Heterometallic 3d-4f complexes are being investigated, for some time, as being useful in molecular magnetism, particularly as single-molecule magnets (SMMs). This interest is primarily because of the possibility of an increased ligand-mediated super-exchange phenomenon between the 3d and 4f metal ions. Such an interaction, apart from bestowing a favorable ground-state spin to the complex, also assists in reducing quantum tunneling of magnetization that is widely prevalent in SMMs making them to lose magnetization. However, assembling both 3d as well as 4f ions using same ligand system is challenging and involves the design of multi-site coordination ligands with specific coordination compartments for the 3d and the 4f metal ions while at the same time allowing these disparate metal ions to be linked to each other through a bridging ligating atom. This review presents a summary of the 3d-4f complexes primarily derived from the author's work while alluding to important examples from the literature. We also provide an outlook for the future design of such complexes.

Bond Forming Reactions Involving Isocyanides at Diiron Complexes

The versatility of isocyanides (CNR) in organic chemistry has been tremendously enhanced by continuous advancement in transition metal catalysis. On the other hand, the urgent need for new and more sustainable synthetic strategies based on abundant and environmental-friendly metals are shifting the focus towards iron-assisted or iron-catalyzed reactions. Diiron complexes, taking advantage of peculiar activation modes and reaction profiles associated with multisite coordination, have the potential to compensate the lower activity of Fe compared to other transition metals, in order to activate CNR ligands. A number of reactions reported in the literature shows that diiron organometallic complexes can effectively assist and promote most of the “classic” isocyanide transformations, including CNR conversion into carbyne and carbene ligands, CNR insertion, and coupling reactions with other active molecular fragments in a cascade sequence. The aim is to evidence the potential offered by diiron coordination of isocyanides for the development of new and more sustainable synthetic strategies for the construction of complex molecular architectures.

Heterometallic ZnII⁻LnIII⁻ZnII Schiff Base Complexes with Linear or Bent Conformation-Synthesis, Crystal Structures, Luminescent and Magnetic Characterization.

A series of racemic, heteronuclear complexes [Zn2Nd(ac)2(HL)2]NO3·3H2O (1), [Zn2Sm(ac)2(HL)2]NO3·3CH3OH·0.3H2O (2), [Zn2Ln(ac)2(HL)2]NO3·5.33H2O (3–5) (where HL is the dideprotonated form of N,N′-bis(5-bromo-3-methoxysalicylidene)-1,3-diamino-2-propanol, ac = acetate ion, and Ln = Eu (3), Tb (4), Dy (5), respectively) with an achiral multisite coordination Schiff base ligand (H3L) were synthesized and characterized. The X-ray crystallography revealed that the chirality in complexes is centered at lanthanide(III) ions due to two vicinally located μ-acetato-bridging ligands. The presented crystals have isoskeletal coordination units but they crystallize in monoclinic (1, 2) or trigonal crystal systems (3–5) with slightly different conformation. In 1 and 2 the ZnII–LnIII–ZnII coordination core is linear, whereas in isostructural crystals 3–5 the chiral coordination cores are bent and lie on a two-fold axis. The complexes 1, 3–5 show a blue emission attributed to the emission of the ligand. For ZnII2SmIII complex (2) the characteristic emission bands of f-f* transitions were observed. The magnetic properties for compounds 1, 4 and 5 are characteristic for the paramagnetism of the corresponding lanthanide(III) ions.

Heterometallic Heptanuclear [Cu5Ln2] (Ln = Tb, Dy, and Ho) Single-Molecule Magnets Organized in One-Dimensional Coordination Polymeric Network.

The reaction of a multisite coordination ligand, LH3, with Cu(II) salts and Ln(NO3)3·nH2O in a 1:2:1 stoichiometric ratio in the presence of triethylamine was found to afford a series of one-dimensional heterometallic [{Cu5Ln2(L)2(μ3-OH)4(ClO4)(NO3)3(OH2)5}(ClO4)2(H2O)x]∞ [Ln = Tb(1), Dy(2) and Ho(3), x = 4.25, 5.5, and 5 for 1-3, respectively] coordination polymers. Complexes 1-3 have been characterized by single crystal X-ray crystallography. The detailed study of the magnetic properties has also been performed and compared with the parent [Cu5Ln2] molecular analogues. The ac susceptibility measurements for complexes 1-3 confirm their SMM behavior with the following characteristics: Δeff/kB = 23.4 K, τ0 = 1.1 × 10-6 s and Δeff/kB = 27.9 K, τ0 = 6.6 × 10-7 s under 0 and 1200 Oe dc fields, respectively for 1; Δeff/kB = 8.3 K, τ0 = 3.1 × 10-6 s for 2 under 0 dc field. For 3, the fast QTM below 4 K prevents the estimation of the SMM energy barrier. Remarkably, the magnetic and SMM properties of the previously reported molecular [Cu5Ln2] analogues are preserved after their assembly in these coordination networks.

The National Trauma Institute: Lessons learned in the funding and conduct of 16 trauma research studies.

To increase trauma-related research and elevate trauma on the national research agenda, the National Trauma Institute (NTI) issued calls for proposals, selected funding recipients, and coordinated 16 federally funded (Department of Defense) trauma research awards over a 4-year period. We sought to collect and describe the lessons learned from this activity to inform future researchers of barriers and facilitators. Fifteen principal investigators participated in semistructured interviews focused on study management issues such as securing institutional approvals, screening and enrollment, multisite trials management, project funding, staffing, and institutional support. NTI Science Committee meeting minutes and study management data were included in the analysis. Simple descriptive statistics were generated and textual data were analyzed for common themes. Principal investigators reported challenges in obtaining institutional approvals, delays in study initiation, screening and enrollment, multisite management, and study funding. Most were able to successfully resolve challenges and have been productive in terms of scholarly publications, securing additional research funding, and training future trauma investigators. Lessons learned in the conduct of the first two funding rounds managed by NTI are instructive in four key areas: regulatory processes, multisite coordination, adequate funding, and the importance of an established research infrastructure to ensure study success. Recommendations for addressing institution-related and investigator-related challenges are discussed along with ongoing advocacy efforts to secure sustained federal funding of a national trauma research program commensurate with the burden of injury.

Deconstructing Black Swans: An Introductory Approach to Inherited Metabolic Disorders in the Neonate.

Inherited metabolic disorders (IMDs) are individually rare but collectively common disorders that frequently require rapid or urgent therapy. This article provides a generalized approach to IMDs, as well as some investigations and safe therapies that may be initiated pending the metabolic consult. An overview of the research supporting management strategies is provided. In addition, the newborn metabolic screen is reviewed. Caring for infants with IMDs can seem difficult because each of the types is rarely seen; however, collectively the management can be seen as similar. When an IMD is suspected, a metabolic specialist should be consulted for expert advice regarding appropriate laboratory investigations and management. Because rapid intervention of IMDs before the onset of symptoms may prevent future irreversible sequelae, each abnormal newborn screen must be addressed promptly. Management can be difficult. Research in this area is limited and can be difficult without multisite coordination since sample sizes of any significance are difficult to achieve.

A highly sensitive and selective assay of doxycycline by dualwavelength overlapping resonance Rayleigh scattering

A dual-wavelength overlapping resonance Rayleigh scattering (DWO–RRS) method was developed and validated for highly sensitive and selective assay of doxycycline residues in several meat samples. The response signals were dependent on the specific multi-site coordination between lanthanum(III) and doxycycline (DOTC). And La(III)–DOTC complex would further aggregate to form [La(III)–DOTC]n nanoparticles, resulting in the occurrence of two new scattering peaks. Notably, with the addition of DOTC, the increments of both of these two wavelengths were proportional to the concentration of DOTC over the ranges of 3.9–4.0×103nmolL−1 (1.7–1.8×103μg/kg). The detection limit of DWO–RRS was 1.1nmolL−1 (0.5μg/kg), which was lower than or comparable to most of the published methods. Additionally, the generating mechanisms of multi-response RRS signals were discussed and a semi-empirical principle was established for better design of multi-response RRS probes.

Syntheses and structures of a family of heterometallic pentanuclear [MnIII3LnNa] (Ln = Dy, Tb, Gd and Nd) complexes: H-bonding reduces the nuclearity from nine to five

The reaction of a multisite coordination ligand (LH3) with LnCl3·6H2O, followed by the addition of Mn(OAc)2·4H2O, sodium azide and pivalic acid in the presence of triethylamine in a 2 : 1 : 1 : 4 : 4 : 6 (LH3 : LnCl3 : Mn(OAc)2 : NaN3 : pivalic acid : Et3N) stoichiometric ratio afforded a series of heterometallic pentanuclear neutral complexes containing a [MnIII3LnNa] core {Ln = Dy (1), Tb (2), Gd (3) and Nd (4)}. The oxidation states of the MnIII ions were confirmed by BVS calculation. All the complexes were characterized by X-ray crystallography. The pentametallic aggregates form a trigonal-bipyramidal geometry in which the three MnIII ions are in the equatorial plane whereas the sodium and lanthanide ions are in the apical positions. Three different types of MnIII ions are present in the complexes and all are in a distorted octahedral geometry. An all-oxygen environment is found to be present around the lanthanides as well as the sodium ions. The lanthanide ion is eight-coordinated and in distorted dodecahedral geometry, while the sodium ion is six-coordinate in a distorted trigonal prismatic geometry in 1–4. The pentanuclear core [MnIII3LnNa] is a subset of one-half of the nonanuclear ensemble, [MnIII6LnNa2]+, reported in literature. We propose that the reduction in the nuclearity of the heterometallic metal ensemble occurs as a result of the influence of hydrogen bonding interactions present in the system.

Linear, Edge‐Sharing Heterometallic Trinuclear [CoII–LnIII–CoII] (LnIII = GdIII, DyIII, TbIII, and HoIII) Complexes: Slow Relaxation of Magnetization in the DyIII Derivative

AbstractThe sequential reaction of a multisite coordination ligand (LH4) with lanthanide (III) nitrates followed by the addition of Co(NO3)2·6H2O in a 4:1:2 ratio in the presence of triethylamine afforded a series of heterometallic, linear trinuclear complexes [Co2Ln(LH3)4]·3NO3 [Ln = DyIII (1), GdIII (2), TbIII (3), and HoIII (4)]. These tricationic complexes contain nitrate counteranions. The cationic portion of these complexes consists of three metal ions that are arranged in a linear fashion; a central LnIII is present between the two terminal CoII ions and is attached to the latter through two phenoxide bridging groups. This arrangement generates two contiguous four‐membered CoLnO2 rings. The CoII ions are six‐coordinate (2N, 4O) in a distorted octahedral geometry, whereas the central lanthanide ion is eight‐coordinate (8O) in a distorted square‐antiprismatic geometry. Magnetic studies of these complexes have been performed and indicate a slow relaxation of the magnetization for the DyIII derivative 1.

2D-Coordination Polymer Containing Interconnected 82-Membered Organotin Macrocycles

A two-dimensional coordination polymer [(n-Bu3Sn)4(μ-L)2(4,4′-bipy)]n (1) was prepared in a reaction between (n-Bu3Sn)2O, (E)-5-(pyridin-4-yl-methyleneamino)isophthalic acid (LH2), and 4,4′-bipyridine (4,4′-bipy). The structure of 1 is built by the interlinking of 82-membered macrocyles. The generation of the 2D coordination polymer is facilitated by the multisite coordination capability of the dianionic ligand (L2–) as well as involvement of 4,4′-bipyridine as an ancillary ligand.

ChemInform Abstract: Pyridyloxy Cyclophosphazenes and Carbophosphazenes: Inorganic Ring‐Supported Coordination Platforms

AbstractReview: 64 refs.

Quantitative analysis of split base station processing and determination of advantageous architectures for LTE

Centralization of the baseband processing in radio access networks may reduce radio site operations costs, reduce capital costs, and ease implementation of multi-site coordination mechanisms such as coordinated multipoint transmission and reception (CoMP). However, the initial architecture proposals for a centralized Long Term Evolution (LTE) deployment using transport of radio samples require a high-bandwidth, low-latency interconnection network. This may be uneconomical, or it may only be cost effective for a limited number of sites. To mitigate that deficiency without sacrificing the benefits of centralized processing, we identified alternative interfacing options between central and remote units. To do so we analyzed possible splits of the Long Term Evolution (LTE) baseband processing chain for their bandwidth and latency requirements. Next, we analyzed the operational impacts of potential splits based on a number of criteria including ease of CoMP introduction, the possibility of realizing pooling gains, and the ability to update the system and introduce new features. Based on our results, we propose architectures that can leverage the benefits of centralization at a much-reduced cost.

Slow Magnetic Relaxation in Co(III)–Co(II) Mixed-Valence Dinuclear Complexes with a CoIIO5X (X = Cl, Br, NO3) Distorted-Octahedral Coordination Sphere

The reaction of the multisite coordination ligand (LH4) with CoX2·nH2O in the presence of tetrabutylammonium hydroxide affords a series of homometallic dinuclear mixed-valence complexes, [Co(III)Co(II)(LH2)2(X)(H2O)](H2O)m (1, X = Cl and m = 4; 2, X = Br and m = 4; 3, X = NO3 and m = 3). All of the complexes have been structurally characterized by X-ray crystallography. Both cobalt ions in these dinuclear complexes are present in a distorted-octahedral geometry. Detailed magnetic studies on 1-3 have been carried out. M vs H data at different temperatures can be fitted with S = 3/2, the best fit leading to D(3/2) = -7.4 cm(-1), |E/D| < 1 × 10(-3), and g = 2.32 for 1 and D(3/2) = -9.7 cm(-1), |E/D| <1 × 10(-4), and g = 2.52 for 2. In contrast to 1 and 2, M vs H data at different temperatures suggest that compound 3 has comparatively little magnetic anisotropy. In accordance with the large negative D values observed for compounds 1 and 2, they are single-molecule magnets (SMMs) and exhibit slow relaxation of magnetization at low temperatures under an applied magnetic field of 1000 Oe with the following energy barriers: 7.9 cm(-1) (τo = 6.1 × 10(-6) s) for 1 and 14.5 cm(-1) (τo = 1.0 × 10(-6) s) for 2. Complex 3 does not show any SMM behavior, as expected from its small magnetic anisotropy. The τo values observed for 1 and 2 are much larger than expected for a SMM, strongly suggesting that the quantum pathway of relaxation at very low temperatures is not fully suppressed by the effects of the applied field.