By adopting a shape-persistent bimetallic design approach, high initial molecular turnover frequencies (up to 14,800 h(-1)) for coupling of CO2 with epoxides in conjunction with (n)Bu4NI, plus excellent yields under mild conditions (1 bar of CO2, 45 °C) have been achieved for catalysts containing cofacial Zn-salphen units.

For binuclear luminescent host systems, cooperativity between metal-organic moieties becomes feasible with regards to photophysical properties and sensing behavior. A new class of conformationally rigid binuclear platinum(II) and zinc(II) complexes bearing tetradentate aromatic Schiff base (salphen) ligands with limited rotational freedom has been prepared and characterized, and the molecular structure of a (Pt-salphen)2 derivative has been determined by X-ray crystallography. Their UV-vis absorption and emission properties have been investigated and are tentatively ascribed to different excited states depending on the metal and the extent of intramolecular π-stacking interactions. Colorimetric and phosphorescent responses by the bis-Pt(II) complexes in the presence of selected metal ions have been observed. The nature of the host-guest interactions has been examined by quantitative binding studies, mass spectrometry and DFT calculations, and through comparisons with control complexes.

Phosphorescent conjugated polymers consisting of alternating p-phenylene-ethynylene and 'para-' or 'meta-type' Pt(II)-salphen luminophore units have been synthesized. Side-arms bearing different substituents (n-alkoxy and acetylated-sugar) have afforded contrasting emission properties that are attributed to the polymer conformation, extent of π-stacking interactions and differences in chemical structure. Intriguing selectivity in luminescent sensing of metal ions has been observed.

A new class of shape-persistent coordination motifs bearing integrated design features that allow reporting of molecular-level perturbations, and their colorimetric and luminescent responses to metal ions, are described.