Comprehensively understanding the steric hindrance effect on the coordination sphere of Pb2+ ions and photophysical nature of two luminescent Pb(ii)-coordination polymers

Abstract

New luminescent Pb(II)-coordination polymers (Pb(II)-CPs), [Pb(2-anc)₂]_n (1) and [Pb(3-qlc)₂(H₂O)₂]_n (2) (2-anc = 2-aminonicotinate, 3-qlc = 3-quinolinecarboxylate), were synthesized by a solvothermal reaction and characterized using microanalysis, IR spectrometry and thermogravimetric analysis. Single crystal structure analysis revealed that the Pb²⁺ ion displays a hemi-directed coordination geometry in 1 and a holo-directed coordination geometry in 2. The difference between the coordination spheres of 1 and 2 is related to the steric hindrance effect of the ligands. A two-dimensional (2D) corrugated layer structure is formed in 1, and the neighboring layers are further extended into a three-dimensional (3D) van der Waals crystal by π⋯π interactions between the pyridyl rings in the neighboring layers. In contrast, a one-dimensional (1D) coordination polymeric chain is formed in 2, and the adjacent chains are connected in a 2D network by hydrogen bonds. The photophysical properties of 1 and 2 were studied at ambient conditions, disclosing that 1 emits phosphorescence at 548 nm with a millisecond-scale emission lifetime and an absolute quantum yield of 2.2%; 2 emits only blue fluorescence with an absolute quantum yield of 3.5% and nanosecond-scale emission lifetime. The reasons for the difference in the photophysical nature of 1 and 2 are discussed in regards to the electron band structure and density of states analysis.