Hybrid Inorganic-Organic Complexes of Zn, Cd, and Pb with a Cationic Phenanthro-diimine Ligand

Funding Information: Financial support from the Academy of Finland (decision 317903, I.O.K.; decision 340584, T.E. and A.J.K.; Flagship Programme, Photonics Research and Innovation PREIN, decision 320166) and computational resources from the Finnish IT Center for Science (CSC) are gratefully acknowledged. Publisher Copyright: © 2022 The Authors. Published by American Chemical Society. The phosphonium-decorated phenanthro-imidazolyl pyridine ligand, LP +Br, readily reacts with zinc(II) and cadmium(II) bromides to give inorganic-organic zero-dimensional compounds [ LP +ZnBr2]2[ZnBr4] ( 1 ) and [( LP +)2Cd2Br4][CdBr4] ( 2 ), respectively, upon crystallization. These salts are moderately fluorescent in the solid state under ambient conditions (λem = 458 nm, φem = 0.11 for 1 ; λem = 460 nm, φem = 0.13 for 2 ). Their emission results from spin-allowed electronic transitions localized on the organic component with the negligible effect of [MBr4]2- and MBr2 units. Contrary to ionic species 1 and 2 , lead(II) bromide affords a neutral and water-stable complex [( LP +)2Pb3Br8] ( 3 ), showing weak room-temperature phosphorescence arising from spin-orbit coupling due to the heavy atom effect. The emission, which is substantially enhanced for the amorphous sample of 3 (λem = 575 nm, φem = 0.06), is assigned to the intraligand triplet excited state, which is a rare phenomenon among Pb(II) molecular materials.