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 [Ag₂X₂(PPh₃)₂(Me₂pyz)]_n (X = I, Br, Cl; Me₂pyz: 2,5-dimethylpyrazine) were prepared together with copper congeners [Cu₂X₂(PPh₃)₂(Me₂pyz)]_n (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. The relaxation in the emissive excited states (ESs) was determined to be more remarkable in silver complexes than in copper complexes despite their isomorphous structures, and the electronic effect of halogenido ligands was comparable to the effect of relaxation in emissive ESs.