Synthesis and Characterization of Self-Assembled Nanoscopic Metallarectangles Capable of Binding Fullerenes with Size-Selective Responses

Abstract

Two new metallarectangles, 4 and 5, were obtained from the self-assembly of areneruthenium-based molecular clips 2 and 3 with a new dipyridyl donor ligand 1 containing a diamide core and ethynyl spacers. The metallarectangles were characterized by multinuclear NMR, electrospray ionization mass spectrometry, and UV-vis spectroscopy, and the molecular structure of 4 was unambiguously determined by single-crystal X-ray diffraction analysis. Because of the presence of an extended π-electron aromatic surface, the tetracene-containing molecular rectangle 5 was capable of binding C60 and C70 fullerenes as quantified by UV-vis, emission, and (1)H NMR experiments, providing an example of a supramolecular host capable of recognizing large guest molecules.

Coordination‐Driven Self‐Assembly of Arene–Ruthenium Compounds

“…Organometallic half‐sandwich complexes based on arene–ruthenium acceptors are not only effective building blocks for metallacycles but they also show interesting electronic, structural, and signaling properties for sensors 63–66. Usually, the internal cavities in macrocycles are well suited to act as receptor sites for small molecules.…”

“…We recently reported various metalla‐assemblies, such as hexanuclear cages and metallarectangles, composed of arene–Ru acceptors and pyridyl donors. We then used these molecules in various anticancer and sensing applications 54–66…”

Ethylene Polymerization Using Site‐Selective Pyridine‐Amide Based Iron Complexes

“…The pyridine‐amide ligand‐based coordination complexes are extensively used for supramolecular structures . Such coordination complexes resulted in precise control over the placement of molecular components resulting in interesting structural topologies and tailor‐made properties …”

Supramolecular architectures with pyridine-amide based ligands: discrete molecular assemblies and their applications

“…Ligand L5 was synthesized in two steps. 37 Initially, the precursor N,N′-bis(4-iodophenyl)terephthalamide was obtained by coupling 4-iodoaniline and terephthaloyl dichloride in CH 2 Cl 2 in the presence of Et 3 N. The resulting product was then coupled with 4-ethynylpyridine in DMF under standard Sonogashira coupling conditions to afford the final ligand L5 (Scheme 1d). Interestingly, L5 is a much extended ligand that also incorporates two electrondeficient alkyne moieties thus suggesting its potential sensing applications.…”

“…[12][13][14] In recent times, various methodologies for the rational design of multi-dimensional structures have been developed, led by the groups of Stang, [15][16][17] Raymond, [18][19][20] Fujita, [21][22][23] Therrien, [24][25][26] and Puddephatt [27][28][29] and adequately followed by others. [30][31][32][33][34][35][36][37][38][39] This rational design strategy allows for a combinatorial molecular library consisting of complementary molecular components that allows one to think retro-synthetically on how best to achieve the geometry of a particular discrete assembly. A large number of intriguing molecular assemblies, such as molecular triangles, squares, rectangles, cages, and metallacycles, have been synthesized using pyridine-amide based ligands and suitable metal ions.…”