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Josef Hamacek

Publications and source records attributed to Josef Hamacek.

7 recordsLinked to original sources
PubMed2006

How to adapt Scatchard plot for graphically addressing cooperativity in multicomponent self-assemblies.

A graphical method has been developed for the reliable detection of cooperativity in polymetallic complexes involving intra- and intermolecular complexation processes. The method relies on the determination of the partial occupancy r(AL)n, which represents the average number of metals bound per preassembled receptor AL(n) made up of n ligands bound to a linker A. We observe nonlinear, i.e., nonstatistical, Scatchard-like plots (r(AL)n/[M] vs r(AL)n) for metal-binding in double-stranded helicates. The present concept is extended to a virtual, pre-organized receptor L(n), in which no specific linker is involved. Applications to several polymetallic helicates reveal the presence of negatively cooperative processes attributed mainly to intermetallic repulsions, in agreement with recent thermodynamic models.

Journal Article↗
PubMed2006

Simple thermodynamics for unravelling sophisticated self-assembly processes.

During the past 15 years, coordination chemistry has rapidly developed toward multicomponent assemblies involving several ligands and metal ions, which are connected via intra- or intermolecular processes. The fascinating structural aspect of these complexation reactions has been early recognized for the design of sophisticated (supra)molecular architectures with novel topologies and functions, while the concomitant energetic part only recently emerged as a potential tools for controlling and programming self-assemblies. In this Perspective, we focus on the modelling of the free energy changes accompanying self-assembly processes. Starting with the original protein-ligand model borrowed from biology, which describes complicated multicomponent assemblies, we present (i) its adaptation to coordination chemistry and (ii) its significance for addressing cooperativity as an extra energy cost resulting from intercomponent interactions. An additional entropic concept arising from the separation of intra- and intermolecular complexation processes is then discussed, together with its explicit consideration for modeling multicomponent complexation reactions. Finally, both aspects (i.e. cooperativity and intra-/intermolecular connections) are combined in the extended site binding model, which is able to dissect free energy changes occurring in sophisticated metal-ligand assemblies with a minimum set of microscopic parameters. Applications to experimental complexation reactions of increasing complexity are systematically discussed, and illustrate the potential and limitations of each model.

Kinetics↗
PubMed2005

A simple thermodynamic model for quantitatively addressing cooperativity in multicomponent self-assembly processes--Part 2: Extension to multimetallic helicates possessing different binding sites.

The extended site-binding model, which explicitly separates intramolecular interactions (i.e., intermetallic and interligand) from the successive binding of metal ions to polytopic receptors, is used for unravelling the self-assembly of trimetallic double-stranded Cu(I) and triple-stranded Eu(III) helicates. A thorough analysis of the available stability constants systematically shows that negatively cooperative processes operate, in strong contrast with previous reports invoking either statistical behaviours or positive cooperativity. Our results also highlight the need for combining successive generations of complexes with common binding units, but with increasing metallic nuclearities, for rationalizing and programming multicomponent supramolecular assemblies.

Journal Article↗
PubMed2005

A simple thermodynamic model for quantitatively addressing cooperativity in multicomponent self-assembly processes--part 1: Theoretical concepts and application to monometallic coordination complexes and bimetallic helicates possessing identical binding sites.

A thermodynamic model has been developed for quantitatively estimating cooperativity in supramolecular polymetallic [M(m)L(n)] assemblies, as the combination of two simple indexes measuring intermetallic (I(c)MM) and interligand (I(c)LL) interactions. The usual microscopic intermolecular metal-ligand affinities (f(i)(M,L)) and intermetallic interaction parameters (uMM), adapted to the description of successive intermolecular binding of metal ions to a preorganized receptor, are completed with interligand interactions (uLL) and effective concentrations (c(eff)), accounting for the explicit free energy associated with the aggregation of the ligands forming the receptor. Application to standard monometallic pseudo-octahedral complexes [M(L)(n)(H2O)(6 - n)] (M = Co, Ni, Hf, L = ammonia, fluoride, imidazole, n = 1-6) systematically shows negative cooperativity (uLL < 1), which can be modulated by the electronic structures, charges, and sizes of the entering ligands and of the metal ions. Extension to the self-assembly of more sophisticated bimetallic helicates possessing identical binding sites is discussed, together with the origin of the positively cooperative formation of [Eu2(L3)3].

Journal Article↗
PubMed2004

A simple thermodynamic model for rationalizing the formation of self-assembled multimetallic edifices: application to triple-stranded helicates.

Reaction of the bis-tridentate ligand bis[1-ethyl-2-[6'-(N,N-diethylcarbamoyl)pyridin-2'-yl]benzimidazol-5-yl]methane (L2) with Ln(CF(3)SO(3))(3).xH(2)O in acetonitrile (Ln = La-Lu) demonstrates the successive formation of three stable complexes [Ln(L2)(3)](3+), [Ln(2)(L2)(3)](6+), and [Ln(2)(L2)(2)](6+). Crystal-field independent NMR methods establish that the crystal structure of [Tb(2)(L2)(3)](6+) is a satisfying model for the helical structure observed in solution. This allows the qualitative and quantitative beta23 (bi,Ln1,Ln2)characterization of the heterobimetallic helicates [(Ln(1))(Ln(2))(L2)(3)](6+). A simple free energy thermodynamic model based on (i) an absolute affinity for each nine-coordinate lanthanide occupying a terminal N(6)O(3) site and (ii) a single intermetallic interaction between two adjacent metal ions in the complexes (DeltaE) successfully models the experimental macroscopic constants and allows the rational molecular programming of the extended trimetallic homologues [Ln(3)(L5)(3)](9+).

Journal Article↗
PubMed2003

Self-assembly mechanism of a bimetallic europium triple-stranded helicate.

We report the self-assembly process of a supramolecular edifice based on the coordination of europium(III) by a ditopic strand L bearing tridentate bis(benzimidazolyl)pyridine subunits. Varying the metal/ligand ratio and using a fruitful combination of electrospray mass spectrometry and absorption spectrophotometry, we characterized three major complexes (EuL(2), Eu(2)L(2), and Eu(2)L(3)) in acetonitrile. Kinetic investigations showed an alternative "braiding" and "keystone" mechanism leading to Eu(2)L(3). The formation mechanism of the dinuclear triple-stranded helicate, which is mainly governed by electrostatic interactions, goes via the "side-by-side" Eu(2)L(2) intermediate. Our thermodynamic and kinetic data allow the prediction of the apparent "magic" self-assembly of Eu(2)L(3) which is fast and efficient only under a strict set of conditions.

Journal Article↗