Metal ion coordination enhancing quantum efficiency of ligand phosphorescence in a double-stranded helical chain coordination polymer of Pb 2+ with nicotinic acid.

A new 1D phosphorescence coordination polymer (CP) [Pb2O(C6H4NO2)2]n (1; C6H4NO2 = nicotinate) was synthesized by a solvothermal reaction and PbO was used as a Pb(ii) source instead of traditional Pb(ii) salts. This remarkably thermal-stable CP crystallizes in the space group I41/a. In the crystal structure of 1, two different Pb(ii) ions show a five-coordinated and hemidirected coordination geometry, two nonequivalent nicotinate ligands link to Pb(ii) ions in μ2-η1:η1 and μ4-η2:η2 modes, and the hemidirected coordination polyhedra of Pb(ii) form a helical lead-oxide chain via an edge-sharing fashion along the c-axis. Under ambient conditions, 1 emits cyan ligand-based phosphorescence with an absolute quantum yield as high as 59.4% and a lifetime of 9.86 ms under UV-light irradiation. Under the same conditions, nicotinic acid emits simultaneously fluorescence and phosphorescence with a total absolute quantum yield of 4.8%. The great enhancement of phosphorescence quantum yield in 1, regarding nicotinic acid, is assigned to the heavy atom effect of Pb(ii) and negligible ππ interaction between pyridyl rings. Noticeably, the vibronic fine structure is observed in the emission spectrum of 1 at room temperature. Additionally, 1 shows thermochromic behavior, and such functionality probably has realistic application in the field of temperature detection.