An integrated study of the organic–inorganic framework material zinc cyclohexane trans‐1,2‐dicarboxylate involving synthesis, structure elucidation, computer simulation, and calorimetry shows that the chiral R,R form (right in picture) is less stable than its racemic R,R/S,S analogue (left) and adopts a layered structure with a fundamentally different topology. The results point to the possibility that the structural diversity of racemic frameworks and their homochiral analogues may be much greater than has hitherto been suspected.

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A detailed study of the ability of pyridine-2,6-dicarboxylic acid (1) and its 4-mono-and 3,4,5-trisubstituted analogues to sensitize emission from Pr 3+ , Nd 3+ , Gd 3+ , Dy 3+ and Er 3+ is presented. Sensitization of Ln 3+ emission was demonstrated via the ligands in all complexes, excluding Gd 3+ , with emission covering the spectral range from 500 nm to 1850 nm obtained with variation of the Ln 3+ ion. From the study of the ligand-based photoluminescence obtained from Gd 3+ -complexes, and the relative ligand and Ln 3+ emission obtained from the other complexes, the singlet and triplet state energies of complexes of (1) are estimated to be at 3.1 eV and 2.6 eV respectively whilst for the 3,5-dibromo-substituted complexes (4) they are at 2.9 eV and 2.3 eV. Hypersensitivity of the Er 3+ 4 I15/2 → 2 H11/2 and 4 I15/2 → 4 G11/2 intraatomic transitions is also observed in the 4-chloro-substituted (3) complex. Enhanced sensitization of Nd 3+ (ca. 5-fold) and Er 3+ (ca. 2-fold) near-infrared emission is demonstrated for complexes of (3) and ( 4) respectively in comparison with those of (1).

Eine integrierte Studie der organisch‐anorganischen Gerüststruktur von Zinkcyclohexan‐trans‐1,2‐dicarboxylat duch Synthese, Strukturaufklärung, Computersimulation und kalorimetrischen Messungen belegt, dass die chirale R,R‐Form (Bild rechts) weniger stabil ist als die racemische R,R/S,S‐Form (links) und eine Schichtstruktur mit anderer Topologie einnimmt. Dies könnte bedeuten, dass die Strukturvielfalt racemischer und homochiraler Gerüstverbindungen sehr viel größer ist als bisher angenommen wurde.