Supramolecular Assemblies Based on Organometallic Quinonoid Linkers: A New Class of Coordination Networks

Abstract

Self-assembly of coordination frameworks exhibiting original architectures is an active area of research. Generally, such assemblies are constructed from organic spacers and transition metals of different geometrical structures. Herein, we report a novel class of supramolecular coordination assemblies with organometallic linkers based on metalated quinonoid and thioquinonoid complexes that serve as spacers. The organometallic ligands are stable and have the general formula [Cp*M(eta(4)-benzoquinone)] (o- and p-benzoquinone, Cp*=C(5)Me(5), M=Rh, Ir) and [Cp*Ir(eta(4)-thiobenzoquinone)] (o- and p-thiobenzoquinone). These units bind through both oxygen or sulfur atoms to metal ions of different coordination geometry, such as Cu(I), Ag(I), and Pt(II), to generate supramolecular coordination networks, with the metalated quinonoid or thioquinonoid linkers acting as backbones and the metal centers as nodes. This novel family of supramolecular assemblies exhibits short pi-pi and MM interactions. These results illustrate successfully the role of the organometallic linkers to produce an impressive range of novel supramolecular architectures that hold promise for the development of functional materials.

Structures, Mechanisms, and Results in Bifunctional Catalysis and Related Species Involving Proton Transfer

“…In efforts to expand our understanding of hydrogen bonding in binfunctional systems, we are looking at other metal fragments. The rich and unusual chemistry enabled by the Cp*Ir fragment [56][57][58][59][60][61] led us to explore it as a platform. In particular, chloro and hydride complexes of Cp*Ir monophosphine fragments have been versatile starting materials or intermediates.…”

Chiral octahedral bimetallic assemblies with Δ‐TRISPHAT as counter anion: Design, anion metathesis, and Cp*Ir as a probe for chiral recognition

“…[11][12][13][14] Some of these complexes exhibited useful luminescent properties. 15,16 Unlike the p-benzoquinone metal complexes the related obenzoquinone compounds can be used as OM-chelates to generate new chiral assemblies.…”

Novel CuI Ethylene Complexes with 6,6′‐Diphenyl‐4,4′‐bipyrimidine Three‐Dimensionally Self‐Assembled by an Intermolecular π‐π Stacking Interaction and a C–H···N Contact

“…Four novel Cu I -Ph 2 bpm/C 2 H 4 adducts that turned out to be three-dimensionally self-assembled by an intermolecular π-π stacking interaction and a C-H···N contact were isolated and characterized by X-ray, 1 H NMR, IR and TG-DTA analyses. There is growing interest in the relevance of weak supramolecular interactions, such as C-H···O and C-H···N hydrogen bonds [33][34][35][36] and π-π interactions, [37][38][39][40] for molecular packing and coordination in the context of supramolecular crystal engineering. It was found that these weak interactions can drive the crystallization process and select a particular molecular structure.…”