The Effect of Solvent and Coordination Environment of Metal Source on the Self-Assembly Pathway of a Pd(II)-Mediated Coordination Capsule

Abstract

The effect of reaction environment on the self-assembly process of an octahedron-shaped PdL capsule was investigated. Quantitative analysis of self-assembly process with H NMR spectroscopy revealed that the self-assembly pathway of the capsule was altered by solvent and a leaving ligand coordinating to the metal source, which are not the components of the final self-assembly. Solvents definitively determine the pathway ofthe self-assembly at a very early stage of the self-assembly. Contrary to the expectation that the weaker the coordination ability of the leaving ligand is, the faster the formation of the final assembly becomes, a leaving ligand with weak coordination ability tends to generate a kinetically trapped species to prevent the capsule formation under mild conditions.

Self-assembly process of a quadruply interlocked palladium cage

“…This is due to the removal of the Py* molecule, whose coordination ability is weaker than 1, during the ionization. Similar results have often been obtained in other Pd(II)-linked coordination self-assemblies [40][41][42] . The result that the signals for Pd 4 1 8 were observed instead of that for Pd 4 1 8 Py* can be interpreted in the same way.…”

Inducing Social Self‐Sorting in Organic Cages To Tune The Shape of The Internal Cavity

“…We previously used density functional theory (DFT) formation energies to explain the thermodynamically preferred cage topologies in the dynamic imine-based selfassembly processes. [41,[57][58][59] Comparing the thermodynamic stabilities of potential cage products can be ag ood guide to selectivity,b ut the reaction outcome can also be affected by factors,s uch as reaction kinetics, [39,[60][61][62][63][64] solvent effects, [65][66][67][68] and the solubilities of the species involved in the equilibrium. [33,40,47] In parallel with the synthetic efforts,w eu sed computational techniques to predict the stability of the different homo-and heteroleptic structures originating from aldehydes B1-B2 and L1-L4.T he experimentally observed outcomes agreed with the relative gas-phase formation energies of the possible Tet 3 Di 6 products,s howing the predictive power of the simple model for the self-sorting behaviour of imine-based organic cages.…”

Chiral self-sorting process in the self-assembly of homochiral coordination cages from axially chiral ligands

“…Then the selfassembly of the ). The coordination ability of Py* is weaker than that of the pyridyl groups in 1, and Py* tends to leave the Pd(II) centres during the ionization process 58 . This tendency was confirmed by the observation of Pd1 S Py* 2 , whose Pd(II) centre is coordinately unsaturated.…”

“…Recently, we have developed a method for the investigation of molecular self-assembly processes based on the concept that the information about the intermediates transiently produced during molecular self-assembly, most of which cannot be detected by spectroscopy, can indirectly be obtained as the average composition of all the intermediates by the quantification of all the substrates and the products (QASAP: quantitative analysis of selfassembly process) [54][55][56][57][58][59][60][61][62][63] . QASAP has enabled us to reveal the selfassembly processes of coordination cages 55,56 , capsules [57][58][59] , sphere 60 and rings [61][62][63] .…”