Development of a Coordination Chemistry-Based Approach for Functional Supramolecular Structures

Abstract

The weak-link approach (WLA) to supramolecular assemblies allows for the design of multimetallic two- and three-dimensional arrays, host-guest architectures, sensors, catalysts, switches, and signal amplification devices. This Account describes the course of our investigations in this area beginning with the development of a chemical tool kit of building blocks consisting of multiple metals and ligands. These building blocks can be rationally mixed and matched to provide structures with a wide range of properties that have been used to develop functional supramolecular architectures, including chemical sensors and allosteric catalysts.

Flexible κ4-PNN′O-tetradentate ligands: synthesis, complexation and structural studies

“…The 1 H NMR and 31 P{ 1 H} NMR spectra were recorded either on Bruker AC250 or DPX-400 FT spectrometers with chemical shifts (δ) reported relative to external TMS or H 3 PO 4 . All NMR spectra (250 or 400 MHz) were recorded in CDCl 3 solutions unless otherwise stated.…”

“…In compounds 11a-11c tetradentate κ 4 34 but significantly shorter than found in Pd{κ 2 -P,N-2-Ph 2 PC 6 H 4 (CH 2 NMe 2 )}Cl(OPh) (P trans to O, 2.088(5) Å vs. P(1) trans to N(1) in 11b]. 35 Crystallographically characterised examples with this combination of donor atoms 35 around the central Ni II , Pd II or Pt II are extremely sparse.…”

The Diphosphorus Complex [Cp2Mo2(CO)4(η2‐P2)] as a Building Block for the Synthesis of Mixed‐Hybrid Coordination Polymers

“…Such derivatives can be classified as “inorganic‐organic” supramolecular complexes as they are usually obtained from two‐component reactions involving the coordination of organic ligands bearing N, O, or S donor atoms to Lewis‐acidic inorganic metal cations. [1h], 2 Due to the lack of P donating connectors and the usual use of simple transition‐metal cations, our group established an alternative approach by utilising organometallic polyphosphorus (P n ) ligand complexes with flexible coordination modes as connectors between metal ions. By using this novel method, it was possible to synthesize one‐ and two‐dimensional coordination polymers,3 vast fullerene‐like supramolecular spherical aggregates,4 and organometallic nanosized capsules 5.…”

Crystallographic Evidence for the Host-Guest Interaction of Metallamacromolecules (A Highlight Review)

“…8 The simplicity of self-assembly has resulted in a plethora of selfassembled complexes having structures containing molecular triangles, squares, higher-order cyclic species, and closed structures with nanometersized cavities. Many impressive examples of metallasupramolecular hosts can be found in studies reported by Lehn, 9 Fujita, 10 Sauvage, 11 Stang,12 Mirkin, 13 Hupp, 14 Lu, 15 Jin 16 and other groups.…”