Synthesis and Photophysical Properties of Silver(I) Coordination Polymers Bridged by Dimethylpyrazine: Comparison of Emissive Excited States between Silver(I) and Copper(I) Congeners.

Highly luminescent silver(I) coordination polymers [AgX(PPh)(Mepyz)] (X = I, Br, Cl; Mepyz: 2,5-dimethylpyrazine) were prepared together with copper congeners [CuX(PPh)(Mepyz)] (X = I, Br). All the complexes showed thermally activated delayed fluorescence from the charge-transfer states in the visible region, from blue to red. The isomorphous relationship among the complexes allowed a detailed discussion of the effect of halogenido ligands and crystal packing on their luminescence energy.

Synthesis and Photophysical Properties of Emissive Silver(I) Halogenido Coordination Polymers Composed of {AgX} Units Bridged by Pyrazine, Methylpyrazine, and Aminopyrazine.

Luminescent silver(I) coordination polymers having a {Ag(μ-X)} rhombic core (X = I, Br) were prepared using pyrazine (pyz), methylpyrazine (Mepyz), and aminopyrazine (ampyz) as bridging ligands. Photophysical measurements show that the complexes were strongly luminescent in the solid state at room temperature; further, the emissive excited state of the pyz and Mepyz complexes was a triplet charge-transfer (CT) excited state, similar to that of their copper(I) congeners, whereas that of the ampyz complex was a intraligand (IL) excited state. The energy of the CT excited state of a silver halogenido complex was revealed to be ca.