scholarly journals Self-Sorting of Two Imine-Based Metal Complexes: Balancing Kinetics and Thermodynamics in Constitutional Dynamic Networks

2019 ◽  
Author(s):  
Jean-François Ayme ◽  
Jean-Marie Lehn
Keyword(s):  
Metal Ions ◽  
Metal Complexes ◽  
Dynamic Networks ◽  
Tetrahedral Complex ◽  
Organic Components ◽  
Factors Influencing ◽  
Ligand Coordination ◽  
Sorting Process ◽  
Reversible Covalent ◽  
Metal Ligand

A major hurdle in the development of complex constitutional dynamic networks (CDNs) is the lack of strategies to simultaneously control the output of two (or more) interconnected dynamic processes over several species, namely reversible covalent imine bonds formation and dynamic metal-ligand coordination. We have studied in detail the factors influencing the fidelity of the self-sorting process (concentration, electronic and steric parameters of the organic components, nature of the metal cations) of 11 constitutional dynamic libraries containing two different amines, aldehydes and metals salts into two imine-based metal complexes, having no overlap in term of their compositions. In all the cases, the outcome of the process was primarily determined by the ability of the octahedral metal ions to select its pair of components from the initial pool of components, the composition of the weaker tetrahedral complex being imposed by the components rejected by the octahedral metal ions. Different octahedral metal ions required different level of precision in the “assembling instructions” provided by the organic components of the CDN to guide it towards a sorted output. The concentration of the reaction mixture, the electronic and steric properties of the initial components of the library were all found to influence the lifetime of unwanted metastable intermediates formed during the assembling of the two complexes.

scholarly journals Self-Sorting of Two Imine-Based Metal Complexes: Balancing Kinetics and Thermodynamics in Constitutional Dynamic Networks

2019 ◽  
Author(s):  
Jean-François Ayme ◽  
Jean-Marie Lehn
Keyword(s):  
Metal Ions ◽  
Metal Complexes ◽  
Dynamic Networks ◽  
Tetrahedral Complex ◽  
Organic Components ◽  
Factors Influencing ◽  
Ligand Coordination ◽  
Sorting Process ◽  
Reversible Covalent ◽  
Metal Ligand

A major hurdle in the development of complex constitutional dynamic networks (CDNs) is the lack of strategies to simultaneously control the output of two (or more) interconnected dynamic processes over several species, namely reversible covalent imine bonds formation and dynamic metal-ligand coordination. We have studied in detail the factors influencing the fidelity of the self-sorting process (concentration, electronic and steric parameters of the organic components, nature of the metal cations) of 11 constitutional dynamic libraries containing two different amines, aldehydes and metals salts into two imine-based metal complexes, having no overlap in term of their compositions. In all the cases, the outcome of the process was primarily determined by the ability of the octahedral metal ions to select its pair of components from the initial pool of components, the composition of the weaker tetrahedral complex being imposed by the components rejected by the octahedral metal ions. Different octahedral metal ions required different level of precision in the “assembling instructions” provided by the organic components of the CDN to guide it towards a sorted output. The concentration of the reaction mixture, the electronic and steric properties of the initial components of the library were all found to influence the lifetime of unwanted metastable intermediates formed during the assembling of the two complexes.

scholarly journals Triple Self-Sorting in Constitutional Dynamic Networks: Parallel Generation of Cu(I), Fe(II) and Zn(II) Imine-Based Metal Complexes

2019 ◽  
Author(s):  
Jean-François Ayme ◽  
Sébastien Dhers ◽  
Jean-Marie Lehn
Keyword(s):  
Metal Complexes ◽  
Driving Forces ◽  
Dynamic Networks ◽  
Dynamic Network ◽  
The Self ◽  
Self Assembling ◽  
Kinetic Trap ◽  
Sorting Process ◽  
Agonistic Relationships ◽  
The Stability

<div>Three imine-based metal complexes, having no overlap in terms of their compositions, have been simultaneously generated from the self-sorting of a constitutional dynamic library (CDL) containing three amines, three aldehydes and three metal salts. The hierarchical ordering of the stability of three metal complexes assembled and the leveraging of the antagonistic and agonistic relationships existing between the constituents within the constitutional dynamic network corresponding to the CDL were pivotal in achieving the desired sorting. The mechanism and the driving forces underlying the self-sorting process have been studied by NMR. The self-sorting of the Fe(II) and Zn(II) complexes was found to depend on an interplay between the thermodynamic driving forces and a kinetic trap involved in their assembling. These results also exemplify the concept of “simplexity” –the fact that the output of a self-assembling system may be simplified by increasing its initial compositional complexity—as the two complexes could self-sort only in the presence of the third pair of organic components, those of the Cu(I) complex.</div><br>

scholarly journals Triple Self-Sorting in Constitutional Dynamic Networks: Parallel Generation of Cu(I), Fe(II) and Zn(II) Imine-Based Metal Complexes

2019 ◽  
Author(s):  
Jean-François Ayme ◽  
Sébastien Dhers ◽  
Jean-Marie Lehn
Keyword(s):  
Metal Complexes ◽  
Driving Forces ◽  
Dynamic Networks ◽  
Dynamic Network ◽  
The Self ◽  
Self Assembling ◽  
Kinetic Trap ◽  
Sorting Process ◽  
Agonistic Relationships ◽  
The Stability

<div>Three imine-based metal complexes, having no overlap in terms of their compositions, have been simultaneously generated from the self-sorting of a constitutional dynamic library (CDL) containing three amines, three aldehydes and three metal salts. The hierarchical ordering of the stability of three metal complexes assembled and the leveraging of the antagonistic and agonistic relationships existing between the constituents within the constitutional dynamic network corresponding to the CDL were pivotal in achieving the desired sorting. The mechanism and the driving forces underlying the self-sorting process have been studied by NMR. The self-sorting of the Fe(II) and Zn(II) complexes was found to depend on an interplay between the thermodynamic driving forces and a kinetic trap involved in their assembling. These results also exemplify the concept of “simplexity” –the fact that the output of a self-assembling system may be simplified by increasing its initial compositional complexity—as the two complexes could self-sort only in the presence of the third pair of organic components, those of the Cu(I) complex.</div><br>

scholarly journals Thermo-responsive light-emitting metal complexes and related materials

2020 ◽  
Vol 7 (18) ◽  
pp. 3258-3281 ◽  
Author(s):  
Rui Li ◽  
Fa-Feng Xu ◽  
Zhong-Liang Gong ◽  
Yu-Wu Zhong
Keyword(s):  
Information Security ◽  
Metal Complexes ◽  
Temperature Sensing ◽  
Design Strategies ◽  
Light Emitting ◽  
Ligand Coordination ◽  
Metal Ligand

This review discusses the fundamentals and design strategies for the development of thermo-responsive metal–ligand coordination materials and the applications of these materials in temperature sensing, bioimaging, information security, etc.

scholarly journals Potentiometric Studies on Transition Metal Complexes of Substituted Derivative of Coumarin-Part 1

2009 ◽  
Vol 6 (4) ◽  
pp. 1121-1124
Author(s):  
K. B. Vyas ◽  
G. R. Jani ◽  
M. V. Hathi
Keyword(s):  
Ionic Strength ◽  
Transition Metal ◽  
Metal Ions ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Sodium Nitrate ◽  
Formation Constants ◽  
Potentiometric Studies ◽  
Factors Influencing ◽  
Binary Complexes

The formation constants of binary complexes of d10metal ions Cu(II), Ni(II), Co(II) and Mn(II) with 3-[{3-(3’-chloro phenyl}-prop-2-enoyl]-4-hydroxy-6-methyl-2H-chromen-2-one have been studied by using Irving-Rossoti method at constant temperature 30±1°C and ionic strength μ=0.1 M dM-3was held constant using sodium nitrate as an electrolyte. The factors influencing formation and stabilities of binary complexes have been discussed.

scholarly journals Enabling Tunable Hydrophilicity of PDMS via Metal-ligand Coordinated Dynamic Networks

2021 ◽  
Author(s):  
Xinyue Zhang ◽  
Ralph Crisci ◽  
John. A Finlay ◽  
Hongyi Cai ◽  
Anthony S. Clare ◽  
...  
Keyword(s):  
Surface Reconstruction ◽  
Dynamic Networks ◽  
Chemical Properties ◽  
Covalent Interaction ◽  
Wide Range ◽  
Ligand Coordination ◽  
Fouling Release ◽  
Surface Modification Techniques ◽  
Physical And Chemical ◽  
Metal Ligand

Polydimethylsiloxane (PDMS) has been widely used in various fields due to its appealing physical and chemical properties. However, its high hydrophobicity not only yields poor adhesion to substrates but also facilitates undesired adsorption of substances such as proteins, biofoulers, etc., which limits the performance and lifetime of PDMS. Moreover, traditional surface modification techniques are often not efficient on PDMS surfaces because of the surface reconstruction. Although new methods involving chemical modification have been developed, most of them require complicated procedures and equipment. To overcome this challenge, we incorporate metal-ligand coordination, a non-covalent interaction bearing polar functionality, into PDMS, which exposes the hydrophilicity progressively upon dynamic bond breakage and reformation. We demonstrate that the hydrophilicity of coordinated PDMS can be tailored by the choice of network structure, counter anions, and metal cations, which yield distinct network dynamics. The wetting mechanism is discussed in the context of chain reconfiguration and surface reconstruction. We also show that a properly designed metal-ligand coordinated PDMS has potential as a superior marine fouling release coating by weakening diatom attachment. Through this paper, we introduce a new concept for tuning material hydrophilicity via dynamic polar functionalities, which is applicable to a wide range of polymers.

scholarly journals Metal complexes of triazine - Schiff bases: Spectroscopic and thermodynamic studies of complexation of some divalent metal ions with 3-(α-acetylethylidenehydrazino)-5,6-diphenyl-1,2,4-triazine

1999 ◽  
Vol 64 (10) ◽  
pp. 621-635 ◽  
Author(s):  
M. Mashaly ◽  
H.A. Bayoumi ◽  
A. Taha
Keyword(s):  
Schiff Base ◽  
Metal Ions ◽  
Metal Complexes ◽  
Water Solution ◽  
Formation Constants ◽  
Divalent Metal ◽  
Divalent Metal Ions ◽  
Different Temperatures ◽  
Metal Ligand ◽  
Cu And Zn

Metal complexes of some divalent metal ions (Co, Ni, Cu and Zn) with 3-(?- acetylethylidenehydrazino)-5,6-diphenyl-1,2,4-triazine (AHDT) as a Schiff-base have been investigated potentiometrically and spectrophotometrically and found to have the stoichiometric formulae 1:1 and 1:2 (M:L). The formation constants of the proton-ligand and metal-ligand complexes have been determined potentiometrically at different temperatures (10, 20, 30, 40 and 50?C) at an ionic strength of 0.1MKNO3 in 75%(v/v) dioxane-water solution. The standard thermodynamic parameters, viz. ?Go, ?Ho, and ?So, for the proton-ligand and the stepwise metal-ligand complexes have been evaluated.

Simultaneous Generation of a [2×2] Grid-like Complex and a Linear Double Helicate: A Three-Level Self-Sorting Process

2019 ◽  
Author(s):  
Jean-François Ayme ◽  
Jean-Marie Lehn ◽  
Corinne Bailly ◽  
Lydia Karmazin
Keyword(s):  
Metal Complexes ◽  
Mass Spectroscopy ◽  
Metal Salts ◽  
Simultaneous Generation ◽  
X Ray ◽  
X Ray Crystallography ◽  
Sorting Process

<div>Two constitutional dynamic libraries (CDLs)—each containing two amines, two dialdehydes and two metal salts—have been found to self-sort, generating two pairs of imine-based metallosupramolecular architectures sharing no component, a [2×2] grid-like complex and a linear double helicate. These CDLs provided unique examples of a three-level self-sorting process, as only two imine-based ligand constituents, two metal complexes and two architectures were selected during their assembling out of all the possible combinations of their initial components. The metallosupramolecular architectures assembled were characterized by NMR, mass spectroscopy, and X-ray crystallography.</div>

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