H2PO4–- and Solvent-Induced Polymorphism of an Amide-Functionalized [Pt(N^C^N)Cl] Complex

A simple [Pt­(N^C^N)­Cl] complex functionalized with an amide group was prepared, and its absorption and emission properties were examined in different solvents in response to various anions. On the one hand, in the presence of H2PO4–, the solution of the complex shows distinct color changes in CH3CN, together with a ratiometric emission change from a green emission band at 537 nm to a deep red emission band at 680 nm. On the other hand, two-step spectral changes were observed in response to H2PO4– in CH2Cl2, with the green emission being attenuated first followed by the appearance of enhanced and yellow-green emissions at a lower-energy region. These recognition processes are highly selective for H2PO4– against other common anions including F–, Cl–, Br–, I–, OAc–, NO3–, and HSO4–. In addition, the platinum complex displays multistage emission polymorphism in mixed CH3CN/H2O solvent of various ratios. The hydrogen-bonding interaction between H2PO4– and the amide unit was confirmed by NMR analysis. In the solid state, this platinum complex emits red light. However, the composite material of the platinum complex with H2PO4– shows purely monomeric yellow emissions. The solid-state materials were further analyzed by single-crystal X-ray and Fourier-transform IR analysis. These studies suggest that this simple platinum complex is useful for the selective recognition of H2PO4– and as solid-state emitting materials with tunable emission colors.