Coordination‐Driven Self‐Assembly of Functionalized Supramolecular Metallacycles: Highlighted Research during 2010–2018

Abstract

During the past few decades, the construction of macrocyclic molecules/complexes has attracted considerable attention because of their wide applications in sensing, catalysis, molecular machine, drug delivery, etc. Coordination‐driven self‐assembly has proven to be a simple yet highly efficient approach for the preparation of various supramolecular metallacycles with the predetermined shapes and sizes as well as the distribution and total number of functional groups. Since the significant progress has been made during the last few years in the field of coordination‐driven self‐assembly, it is time to summarize the recent development in coordination‐driven self‐assembly of functionalized supramolecular metallacycles. In this review, we will highlight some recent advances concerning the preparation of functionalized supramolecular metallacycles via coordination‐driven self‐assembly between the year 2010–2018. In addition, the properties and the applications of these metallacycles in the areas of photo‐ and electrochemistry, sensing, supramolecular gel, biological applications, etc. will be also discussed.

Semicoordination Bond Breaking and Halogen Bond Making Change the Supramolecular Architecture of Metal-Containing Aggregates

“…Supramolecular aggregates involving metal species demonstrate great diversities of applications spanning from catalysis to materials science, − photophysics, ,, and bioinorganic chemistry. , As compared to purely organic compounds, metal complexes exhibiting more centers are capable of forming noncovalent interactions. This makes the control of the formed supramolecular aggregates more complicated; at the same time, this diversity opens up broader opportunities for the fine-tuning of target architectures and, eventually, properties.…”

“…Supramolecular aggregates involving metal species demonstrate great diversities of applications spanning from catalysis to materials science, 1−5 photophysics, 2,6,7 and bioinorganic chemistry. 2,8 As compared to purely organic compounds, metal complexes exhibiting more centers are capable of forming noncovalent interactions.…”

Delocalization of the Excited State and Emission Spectrum of the Platinum(II) Bipyridine Complex in Crystal: Periodic QM/MM Study

“…Crystal effects observed in platinum­(II) complexes with conjugated aromatic ligands have been widely studied in the last decade because they are promising candidates for luminescence materials useful for light-emitting devices and molecular sensors, as reviewed recently. − Most of the platinum­(II) complexes exhibit an intense phosphorescence spectrum from the triplet excited state in a crystal, although they are weakly emissive or not at all in the solution phase. ,,,, Such a phenomenon is named aggregation-induced or assembly-induced phosphorescence (AIP), which is one of the important crystal effects. This interesting AIP has been discussed as a result of (i) the rigidification of the excited state in crystal and/or (ii) the presence of metallophilic interaction in crystal.…”

Clickable Norbornene-Based Zirconium Carboxylate Polyhedra

“…When these building blocks are modified in ways that do not disrupt coordination, the resulting metallacycles or cages can be decorated with a wide variety of functional groups. Thus, ligand functionalization has been explored extensively by Stang, Fujita, Yang, and more as an effective strategy for altering the physicochemical properties of the resultant MOPs. − Although a general feature of these self-assemblies is that they possess modular syntheses, it should be noted that ligand modifications may require multistep, low-yielding syntheses and challenging purifications. , Nonetheless, there are many examples of functionalizations, for instance, on the well-studied copper isophthalate paddlewheel-based MOPs, − and platinum or palladium pyridyl cages and metallacycles. , The ligand functionalization strategy may be generalized beyond these cores, which suffer from poor hydrolytic stability , and high cost, respectively.…”

“…When these building blocks are modified in ways that do not disrupt coordination, the resulting metallacycles or cages can be decorated with a wide variety of functional groups. Thus, ligand functionalization has been explored extensively by Stang, 8 Fujita, 9 Yang, 10 and more as an effective strategy for altering the physicochemical properties of the resultant MOPs. 11−18 Although a general feature of these self-assemblies is that they possess modular syntheses, it should be noted that ligand modifications may require multistep, lowyielding syntheses and challenging purifications.…”