Solution properties of trivalent lanthanide trinuclear complexes with ligand 1,3,5-triamino-1,3,5-trideoxy-cis-inositol

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

“…Although this approach has been shown to be adequate 1) for modeling the formation of linear triple-stranded helicates and two-dimensional sandwich complexes shown in Figure 1, [2,[5][6][7] and 2) for assigning negative cooperativity to the successive binding of metal ions in these complexes, it fails to give interpretable free energy of complexation (including desolvation) for each site Dg Conversely, the same reasoning can be applied when the role of ligands and metal ions are reversed. The final microspecies M m L n can be thus alternatively considered as being made up of n rigid monotopic ligands coordinated to a preorganized array of m metal ions exhibiting a maximum of p coordination sites [n p equilibrium in Eq.…”

“…[6,7] 2005 cesses, we considered preorganized rigid receptors L n made up of n parallel ligand strands and providing a maximum of p binding sites. [2,5,6] The associated free energy DG({s i }) for the complexation of m metal ions (m p) to this receptor in the microspecies M m L n [equilibrium in Eq.…”

“…[5,6] Finally, the site-binding model was successfully used [2,6] for two-dimensional sandwich complexes with lanthanides (Figure 1c). [7] The three equidistant binding sites in these triangular receptors are again characterized by standard microscopic intermolecular affinities Dg M = ÀRTln(k M ) and intermetallic interactions DE MM . However, the lack of accessible macroscopic formation constants for any thermodynamic intermediate prevents the eventual separation of these two parameters.…”

A Simple Thermodynamic Model for Quantitatively Addressing Cooperativity in Multicomponent Self‐Assembly Processes—Part 2: Extension to Multimetallic Helicates Possessing Different Binding Sites

“…Twodimensional arrays of metal ions connected by bi-dimensional ligands, [17] and three-dimensional systems, pertinent to cages or clusters, can be easily amenable to modeling, according that their thermodynamic stabilities are available. [18] …”

Lanthanide-Containing Molecular and Supramolecular Polymetallic Functional Assemblies

“…177 Lanthanide-templated reactions may also be used to produce polymetallic complexes, especially with cyclic Schiff bases. 178 Finally, careful design of functional 4f-4f edifices may take advantage of self-assembly processes, for instance, with H 5 L40 (Chart 6) to yield homo-and hetero-dimetallic chelates 24d or with L26-L30, 76 L36,…”