Selective Self-Assembly of a Rectangular Ruthenium Supramolecule from an Unsymmetrical Bridging Unit

Abstract

Herein, we report the synthesis of an unsymmetrical diruthenium bridging unit containing a multidentate oxamate ligand and the subsequent formation of a rectangular supramolecule. The reaction of oxamate 1, 2-((4-bromo-2,6dimethylphenyl)amino)-2-oxo-acetic acid, and [(p-cymene)RuCl 2 ] 2 affords a novel unsymmetrical diruthenium acceptor clip 2, where two ruthenium metal centers are ligated with either [O,O] or [N,O].The molecular clip 2 and bipyridine donor selfassemble to form two-dimensional rectangular supramolecule 3. Self-assembly can produce seven possible isomers depending on the position of the substituted bromoaryl groups. However, 1 H NMR spectroscopic investigation indicated only two different isomers in the reaction mixture. A single isomer is isolated via crystallization, and X-ray crystallography confirms that the product is a C 1 symmetric two-dimensional rectangular supramolecule, in which two bromoaryl groups are located in the farthest position from each other. Theoretical calculations suggest that the self-assembly of supramolecule 3 occurred via 1:1 adducts of the diruthenium molecular clip and bipyridine as an intermediate to predominantly form a single isomer.

Modular synthesis of antimalarial quinoline-based PGM metallarectangles

“…), due to the stretching vibrations of the triflate anions. These assignments are well documented in literature [67][68][69] and support the formation of the cationic assemblies as their triflate salts. ESI-MS analysis further supports the formation of metallarectangles 2c, 2d, 3c, and 3d.…”

Step‐By‐Step Tips to Grow X‐Ray Quality Single Crystals of Metal Macrocyclic Complexes

“…Some studies have reported the successful growth of crystals at temperatures as low as −20 °C. [ 37–38 ]…”

“…Some studies have reported the successful growth of crystals at temperatures as low as −20 °C. [37][38] With both methods, if a sufficient quantity of the sample is present, performing different sets of experiments simultaneously using different solvent combinations is highly recommended as it increases the success rate and saves time. If crystals are not formed within weeks, all samples should be gathered, and other solvent combinations should be tried.…”

Synthesis and Electrochemical Properties of Mixed‐Metal Triangular Complexes Based on Ferrocene‐Based Ligands and Dinuclear Arene Ruthenium Building Blocks

“…These structures have been complexed with appropriate multidentate ligands to form metallocycles and metallocages with guest-inclusion ability. [29][30][31][32][33][34][35][36][37][38][39][40] The sizes of the resulting metallocycles and metallocages are strategically adjusted by changing the size of the linkers and the length and shape of the ligand.…”

“…Dinuclear arene ruthenium, in which two piano‐stools are joined with anilato, oxalato or related bis‐bidentate linkers, have also been reported. These structures have been complexed with appropriate multidentate ligands to form metallocycles and metallocages with guest‐inclusion ability [29–40] . The sizes of the resulting metallocycles and metallocages are strategically adjusted by changing the size of the linkers and the length and shape of the ligand.…”