Dynamic Coordination Chemistry Research Articles

Interface Coordination Stabilizing Reversible Redox of Zinc for High-Performance Zinc-Iodine Batteries.

Aqueous Zn batteries (AZBs) have attracted extensive attention due to good safety, cost-effectiveness, and environmental benignity. However, the sluggish kinetics of divalent zinc ion and the growth of Zn dendrites severely deteriorate the cycling stability and specific capacity. The authors demonstrate modulation of the interfacial redox process of zinc via the dynamic coordination chemistry of phytic acid with zinc ions. The experimental results and theoretical calculation reveal that the in-situ formation of such inorganic-organic films as a dynamic solid-electrolyte interlayer is efficient to buffer the zinc ion transfer via the energy favorable coordinated hopping mechanism for the reversible zinc redox reactions. Especially, along the interfacial coating layer with porous channel structure is able to regulate the solvation structure of zinc ions along the dynamic coordination of the phytic acid skeleton, efficiently inhibiting the surface corrosion of zinc and dendrite growth. Therefore, the resultant Zn anode achieves low voltage hysteresis and long cycle life at rigorous charge and discharge circulation for fabricating highly robust rechargeable batteries. Such an advanced strategy for modulating ion transport demonstrates a highly promising approach to addressing the basic challenges for zinc-based rechargeable batteries, which can potentially be extended to other aqueous batteries.

Cover Feature: Dynamic Coordination Chemistry of Fluorinated Zr‐MOFs: Synthetic Control and Reassembly/Disassembly Beyond de Novo Synthesis to Tune the Structure and Property (Chem. Eur. J. 37/2020)

Cover Feature: Dynamic Coordination Chemistry of Fluorinated Zr‐MOFs: Synthetic Control and Reassembly/Disassembly Beyond de Novo Synthesis to Tune the Structure and Property (Chem. Eur. J. 37/2020)

Dynamic Coordination Chemistry of Fluorinated Zr-MOFs: Synthetic Control and Reassembly/Disassembly Beyond de Novo Synthesis to Tune the Structure and Property.

Known for excellent stability, porosity and functionality, the high-valent Zr4+ metal-organic frameworks (Zr-MOFs) still meets synthetic challenge in modulating the strength of Zr-Ocarboxylate linkage. Herein we explore the unusual coordination dynamics of fluorinated Zr-MOFs by designing two trifluoromethyl modified ligands with distinct geometry preference to form a family of thermodynamic and kinetic products. The low-connecting kinetic Zr-MOFs possess substitutable coordination sites to endow Zr6 -cluster with extra dynamic behaviors, thus opening a post-synthetic pathway to sequential reassembly/disassembly processes. Comprehensive factors, including ligand geometry, Zr6 -cluster connectivity, acid modulator and reaction temperature/concentration, have been studied for controllable syntheses. The stability, hydrophobicity and gas adsorption/separation properties of obtained Zr-MOFs are explored. This work sheds light on the understanding of the dynamic coordination chemistry of Zr-MOFs beyond strong Zr-O bond, which poses a versatile platform for modification and functionalization of Zr-MOFs.

Simultaneous CO2 capture and metal purification from waste streams using triple-level dynamic combinatorial chemistry.

A reduction in CO2 emissions is required to mitigate global warming. Post-combustion carbon capture is one of the most developed technologies that has the potential to meet this goal, but its cost prevents its widespread use. A different approach would be to use CO2 directly as it is captured, before it is stored. Here we explore spontaneous CO2 fixation by industrial polyamines as a strategy to generate dynamic libraries of ligands for metal separation and recovery. We identify the CO2 loadings and solvents promoting the optimal precipitation of each metal from the dynamic libraries of complexes. We demonstrate the separation of lanthanum and nickel using the exhaust gas of an internal combustion engine vehicle, and show that the three metal constituents of the La2Ni9Co alloys used to manufacture the batteries of electric vehicles can be separated and recovered by successive CO2-induced selective precipitations. Beyond the concept of CO2-sourced multi-level dynamic coordination chemistry, this study provides a potential framework for integrated CO2 capture and use through sustainable processes.

Dynamic Coordination Chemistry Enables Free Directional Printing of Biopolymer Hydrogel

Three-dimensional (3D) printing is a promising technology to develop customized biomaterials in regenerative medicine. However, for the majority of printable biomaterials (bioinks) there is always a compromise between excellent printability of fluids and good mechanical properties of solids. Three-dimensional printing of soft materials based on the transition from a fluid to gel state is challenging because of the difficulties to control such transition as well as to maintain uniform conditions three-dimensionally. To solve these challenges, a facile chemical strategy for the development of a novel hydrogel bioink with shear-thinning and self-healing properties based on dynamic metal–ligand coordination bonds is presented. The noncovalent cross-linking allows easy extrusion of the bioink from a reservoir without changing of its bulk mechanical properties. The soft hydrogel can avoid deformation and collapse using omnidirectional embedding of the printable hydrogel into a support gel bath sharing the same ...

Structural Transformation and Stabilization of Metal–Organic Motifs Induced by Halogen Doping

AbstractThe structural transformation of supramolecular nanostructures with constitutional diversity and adaptability by dynamic coordination chemistry would be of fundamental importance for potential applications in molecular switching devices. The role of halogen doping in the formation of elementary metal–organic motifs on surfaces has not been reported. Now, the 9‐ethylguanine molecule (G) and Ni atom, as a model system, are used for the structural transformation and stabilization of metal–organic motifs induced by iodine doping on Au(111). The iodine atoms are homogeneously located at particular hydrogen‐rich locations enclosed by G molecules by electrostatic interactions, which would be the key for such an unexpected stabilizing effect. The generality and robustness of this approach are demonstrated in different metal–organic systems (G/Fe) and also by chlorine and bromine.

Structural Transformation and Stabilization of Metal–Organic Motifs Induced by Halogen Doping

The structural transformation of supramolecular nanostructures with constitutional diversity and adaptability by dynamic coordination chemistry would be of fundamental importance for potential applications in molecular switching devices. The role of halogen doping in the formation of elementary metal-organic motifs on surfaces has not been reported. Now, the 9-ethylguanine molecule (G) and Ni atom, as a model system, are used for the structural transformation and stabilization of metal-organic motifs induced by iodine doping on Au(111). The iodine atoms are homogeneously located at particular hydrogen-rich locations enclosed by G molecules by electrostatic interactions, which would be the key for such an unexpected stabilizing effect. The generality and robustness of this approach are demonstrated in different metal-organic systems (G/Fe) and also by chlorine and bromine.

A general route to chiral nanostructures from helical polymers: P/M switch via dynamic metal coordination

Macroscopically enantiomeric chiral nanospheres made from P or M helical polymer metal complexes can be obtained via dynamic coordination chemistry.

Constitutional Dynamics of Metal-Organic Motifs on a Au(111) Surface.

Constitutional dynamic chemistry (CDC), including both dynamic covalent chemistry and dynamic noncovalent chemistry, relies on reversible formation and breakage of bonds to achieve continuous changes in constitution by reorganization of components. In this regard, CDC is considered to be an efficient and appealing strategy for selective fabrication of surface nanostructures by virtue of dynamic diversity. Although constitutional dynamics of monolayered structures has been recently demonstrated at liquid/solid interfaces, most of molecular reorganization/reaction processes were thought to be irreversible under ultrahigh vacuum (UHV) conditions where CDC is therefore a challenge to be achieved. Here, we have successfully constructed a system that presents constitutional dynamics on a solid surface based on dynamic coordination chemistry, in which selective formation of metal-organic motifs is achieved under UHV conditions. The key to making this reversible switching successful is the molecule-substrate interaction as revealed by DFT calculations.

Constitutional Dynamics of Metal–Organic Motifs on a Au(111) Surface

AbstractConstitutional dynamic chemistry (CDC), including both dynamic covalent chemistry and dynamic noncovalent chemistry, relies on reversible formation and breakage of bonds to achieve continuous changes in constitution by reorganization of components. In this regard, CDC is considered to be an efficient and appealing strategy for selective fabrication of surface nanostructures by virtue of dynamic diversity. Although constitutional dynamics of monolayered structures has been recently demonstrated at liquid/solid interfaces, most of molecular reorganization/reaction processes were thought to be irreversible under ultrahigh vacuum (UHV) conditions where CDC is therefore a challenge to be achieved. Here, we have successfully constructed a system that presents constitutional dynamics on a solid surface based on dynamic coordination chemistry, in which selective formation of metal–organic motifs is achieved under UHV conditions. The key to making this reversible switching successful is the molecule–substrate interaction as revealed by DFT calculations.

A New Binding Mode in the Dynamic Coordination Chemistry of Porphyrins

In our on-going research program dedicated to the coordination of various cations of medical interests, we have been studying different types of porphyrinic architectures.1 Among these cations, bismuth appears as a plausible candidate for alpha-radiotherapy.2 Considering the decay scheme of its 213 isotope, it is obvious that the coordination chemistry of bismuth3 and lead4 and to some extent, thallium are somehow related and exhibit some similarities. For instance, we have shown that an unprecedented transmetalation mechanism involving a daughter radionuclide is expected to increase the rate of 213Bi incorporation leading to 1Bi.5 Moreover, we will detail and demonstrate that this peculiar behaviour is rationalized by a translocation-coupled transmetalation mechanism, leading to the formation of a dinuclear complex in which coexist the long-known out-of-plane (OOP) coordination mode and the newly reported hanging-atop (HAT) coordination mode.6 This HAT binding mode is found in both homo- and heterobimetallic complexes with lead and bismuth (see both X-ray structures above) and represents the prerequisite for metal migration processes according to which these dinuclear complexes behave as allosteric Newton’s Cradle-like devices (NCD).7 This NCD behaviour can be extended to other metal complexes and controlled and/or initiated in different ways.8 1. Lemon, CM; Brothers PJ.; Boitrel B. Dalton Trans. 2011, 40, 6591-6609. 2. Yao Z; Zhang M; Garmestani K; Axworthy DB; Mallett RW; et al. Clin. Cancer Res. 2004, 10, 3137-3146. 3. a) Michaudet L; Richard P; Boitrel B. Chem. Commun. 2000, 1589-1590. b) Boitrel B; Breede M.; Brothers PJ; Hodgson M; Michaudet L; Rickard CEF; Al Salim N Dalton Trans. 2003, 1803-1807.c) Halime Z; Michaudet L; Razavet M; Ruzié C; Boitrel B. Dalton Trans. 2003, 4250-4254. (d) Boitrel B; Halime Z; Michaudet L; Lachkar M; Toupet L. Chem. Commun. 2003, 2670-2671. (e) Halime Z; Lachkar M; Roisnel T; Furet E ; Halet J-F; Boitrel B, Angew. Chem. Int. Ed., 2007, 46, 5120-5124. 4. Halime Z; Michaudet L; Lachkar M; Brossier P; Boitrel B. Bioconjugate Chem., 2004, 15, 1193-1200. 5. Le Gac, S.; Najjari, B.; Motreff, N.; Remaud-Le Saec, P.; Faivre-Chauvet, A.; Dimanche-Boitrel, M.-T.; Morgenstern, A.; Bruchertseifer, F.; Lachkar, M.; Boitrel, B. Chem. Commun. 2011, 47, 8554 - 8556. 6. Le Gac S.; Najjari B.; Fusaro L.; Roisnel T.; Dorcet V.; Luhmer M.; Furet E.; Halet J.-F.; Boitrel B. Chem. Commun., 2012, 48, 3724-3726. 7. Najjari B.; Le Gac S.; Roisnel T.; Dorcet V.; Boitrel B. J. Am. Chem. Soc., 2012, 134, 16017-16032 . 8. a) Le Gac, S.; Dorcet, V.; Fusaro, L.; Boitrel, B., Chem. Eur. J. 2013, 19, 13376-13386. b) Le Gac, S.; Najjari, B.; Dorcet, V.; Roisnel, T.; Fusaro, L.; Luhmer, M.; Furet, E.; Halet, J.-F.; Boitrel, B., Chem. Eur. J. 2013, 19, 11021-11038. c) Le Gac, S.; Fusaro, L.; Roisnel, T.; Boitrel, B., J. Am. Chem. Soc. 2014, 136, 6698-6715. Figure 1

Macrocycles, catenanes, oligomers and polymers in gold chemistry

A critical review is given of the chemistry of macrocycles, catenanes, oligomers and polymers in gold chemistry. Because gold centres are typically labile towards ligand substitution, there may be an easy equilibrium between the cyclic and linear oligomeric or polymeric forms and the preferred products of self-assembly are usually determined by thermodynamic control. The ways in which the self-assembly of complex structures from simple building blocks by dynamic coordination chemistry can be manipulated by ligand design or by the use of secondary bonding forces is emphasized (39 references).

Self-Assembly of Polymers through Dynamic Coordination Chemistry and Hydrogen Bonding: Polymers from Mercury(II) Halides and Bis(amidopyridine) Ligands

The synthesis of hybrid organic–inorganic polymers by combination of mercury(II) halides with the ligand 1,5-bis(isonicotinamido)naphthalene, C10H6(NHCO-4-C5H4N)2, 1. The compounds of formula [HgX2(1)] form either linear (X = Cl, Br) or zig-zag (X = I) polymers and contain tetrahedral mercury(II) centers with bridging ligands 1. The polymers are further assembled by hydrogen bonding between amide groups. When X = Cl or Br, two-dimensional sheet structures are formed whereas, when X = I, a three-dimensional network is formed. A new polymeric form of [HgCl2(Me2SO)] is also described.

Advances in Organometallic Polymers, Ring-Opening Polymerization and the Self-Assembly of Supramolecular Polymers

A personal account is given of the synthesis and properties of polymers and networks containing late transition metal centers in the backbone, especially by using ring-opening polymerization of macrocycles and/or the techniques of supramolecular chemistry. Using these methods, coupled with dynamic coordination chemistry, polymers can be assembled into unusual sheet or network structures by using ligands with hydrogen bonding substituents, or by secondary bonding between inorganic centers. Complexes containing racemic binaphthyl groups in the ligands may self-assemble selectively to give homonuclear or heteronuclear polymers. Bicyclic metal complexes can undergo single ring-opening to form chains or double ring-opening to form sheets.

Self-assembly using dynamic coordination chemistry and hydrogen bonding: mercury(II) macrocycles, polymers and sheets.

The self-assembly of extended metal-containing arrays is described based on dynamic coordination chemistry at mercury(II) with bis(amidopyridyl) ligands to form macrocycles, polymers, or sheets which can be further organized by hydrogen bonding between amide substituents. The ligands 1,2-C6H4[NHC(O)-4-C5H4N]2, 1, 1,2-C(6)H(4)[C(O)NHCH(2)-4-C(5)H(4)N](2), 2, and 1,2-C(6)H(4)[CH(2)C(O)NHCH(2)-4-C(5)H(4)N]2, 3 can adopt polar conformations and so can confer helicity in their complexes. Several macrocycles of formula [(HgX(2))(2)(micro-LL)(2)] (LL = 1, 2), with tetrahedral mercury(II) centers, were prepared in which individual molecules are further self-assembled via hydrogen bonding in the solid state to form one- or two-dimensional polymers or sheets. In one case, a one-dimensional polymer [((HgX2)-(mu-3))n] was formed. It is shown that the mercury(II) centers can be six-coordinate in forming the sheet structure [((HgX2)(mu-2)2)n], in which there are particularly large pores.