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Updated: May 5, 2026

Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of ChalcogenidoplumbatesII or IV
Published on: December 29, 2016
Structure and emission studies of dimorphic crystals of [PtBr2(5,5'-bis(CF3CH2OCH2)-2,2'-bpy)] (1)
Norman Lu1, Lauren M Hight, David R McMillin
1Institute of Organic and Polymeric Materials, National Taipei University of Technology, Taipei 106, Taiwan. normanlu@ntut.edu.tw.
Abstract:
The yellow (1y) and orange (1o) crystalline polymorphs of [PtBr2(5,5'-bis(CF3CH2OCH2)-2,2'-bipyridine)] exhibit surprisingly short nearest neighbour Pt···Pt separations of 3.526 Å and 3.590 Å, respectively, at 295 K. Both distances are much shorter than those found in structures of the unsubstituted [PtBr2(2,2'-bipyridine)] analogue. Consistent with a linear chain structure in 1o and dimer formation in 1y, both solids exhibit emission spectra shifted to much longer wavelengths than that exhibited by the monomer in a low-temperature glass. Furthermore, the emission spectra of 1o and 1y shift to even longer wavelengths as the temperature decreases and the Pt···Pt separations contract. Till now delocalized emission of this type has been considered to be restricted to [PtCl2(diimine)] systems and implausible in PtBr2-containing analogues for steric reasons. Ironically, in the system at hand the bulky 5,5'-substituents apparently promote delocalization of the emission by forming a network of hydrogen-bonding-like C-H···F-C interactions that help shape the packing.
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