Synthesis, characterization and electrochemiluminescent properties of cyclometalated platinum(ii) complexes with substituted 2-phenylpyridine ligands†
Chunxiang Li,Shuqin Wang,Yangmei Huang,Bin Zheng,Ziqi Tian,Yonghong Wen,Feng Li
Dalton Transactions Pub Date : 12/19/2012 00:00:00 , DOI:10.1039/C2DT32466K
Abstract

Two neutral cyclometalated platinum(II) complexes, Pt(DPP)(acac) and Pt(BPP)(acac) (DPP = 2,4-diphenylpyridine, BPP = 2-(4-tert-butylphenyl)-4-phenylpyridine, acac = acetylacetone), have been synthesized and characterized by 1H NMR spectroscopy, mass spectrometry, elemental analyses and by X-ray crystallography for Pt(DPP)(acac). Electrogenerated chemiluminescence (ECL) of the two complexes in the absence or presence of coreactant tri-n-propylamine (TPrA) in different solvents (CH3CN, CH2Cl2, DMF, CH3CN/H2O (V, 50 : 50)) has been studied. The ECL spectra are identical to their own PL spectra, indicating that ECL processes lead to the same metal-to-ligand charge-transfer (3MLCT) excited state that is generated by light excitation. The ECL potentials of Pt(DPP)(acac) and Pt(BPP)(acac)/TPrA in CH3CN and CH3CN/H2O solution were at ∼0.75 V vs. SCE, and significantly negatively shifted by about 0.6 V compared to that of the Ru(bpy)32+/TPrA system. The ECL quantum efficiencies of the complexes are comparable to that of the Ru(bpy)32+/TPrA system. The significant increase of the ECL signal in the coreactant system is due to the formation of the strongly reducing intermediate TPrA˙. It is noteworthy that the ECL efficiencies of the synthesized compounds are much higher than that of the tridentate polypyridyl ligands.

Graphical abstract: Synthesis, characterization and electrochemiluminescent properties of cyclometalated platinum(ii) complexes with substituted 2-phenylpyridine ligands