Energy transfer in metal-exchange binuclear complexes covalently linked by asymmetric ligands

Nitrogen complexation with pi-conjugated ligands is an effective strategy for synthesizing luminescent molecules. The asymmetric bridging ligands L (L1 and L2) have been designed. The terminal chelating sites of the L1 and L2 bridging ligands consisted of 2,2 '-bipyridine (bpy) and 1,10-phenanthroline moieties (where L = L1 and L2; L1 = 2-(3-((4-([2,2 '-bipyridin]-6-yl)benzyl)oxy)phenyl)-1H-imidazo[4,5-f][1,10]phenanthroline and L2 = 2-(3-((4-(6-phenyl-[2,2 '-bipyridin]-4-yl)benzyl)oxy)phenyl)-1H-imidazo[4,5-f][1,10]phenanthroline). The full use of the synthetic strategy of the complexes as ligands and complexes as metals was expected to successfully design and synthesize a series of conjugated metal-exchange complexes linked by the asymmetric bridging ligands L1 and L2. These compounds included monometallic complexes Ru(L) and (L)Ru (C1, C2, C7, and C8), homometallic complexes Ru(L)Ru (C3 and C4), and heterometallic complexes Os(L)Ru and Ru(L)Os (C5, C6, C9, and C10) with Ru- or Os-based units. C3-C10 complexes exhibited various degrees of octahedral distortion around the Ru(ii) or Os(ii) center, which was consistent with the optimized geometry of the coordination complexes based on density functional theory calculation. These complexes exhibited intense spin-allowed ligand-centered transitions with high absorbance at around 288 nm upon absorbing visible light. Notably, all complexes exhibited spin-allowed metal-to-ligand charge transfer absorption of the Ru-based units in the 440-450 nm range. In addition, the heterometallic C5, C6, C9, and C10 complexes showed absorption of the Os-based units in the range of 565-583 nm. The intramolecular energy transfer of C3 and C5 was briefly discussed by comparing the emission intensity of monometallic C1 and C2 to that of binuclear complexes C3 and C5, respectively. The results indicated that the intramolecular energy transfer of the Ru(ii)/Os(ii) polypyridine complexes proceeded from the Ru(ii)- to the Os(ii)-based units in the heterometallic C5 and C6 complexes. The asymmetric heterometallic C5 polymer presents photo-induced intramolecular energy transfer from the high energy Ru-based 3MLCT state to the low energy Os-based unit.

Automated summary

Complexation of nitrogen with pi-conjugated ligands is an effective strategy for synthesizing luminescent molecules. In this study, asymmetric bridging ligands L1 and L2 were designed to successfully synthesize a series of conjugated metal-exchange complexes. These complexes exhibited strong absorption in the visible range and spin-allowed metal-to-ligand charge transfer absorption.