Preparation And Photophysical Properties Of Copper (i) Phosphorescent Metal-organic Materials

The Cu(Ⅰ) complexes have attracted general attention because of their various geometry structure and interesting optical properties, and many Cu(Ⅰ) complexes with polynuclear or phenathroline have been reported. But, luminescent Cu(Ⅰ) complexes containing bipyridine and PPh3 ligands are still rare. Here we synthesized a series of Cu(Ⅰ) complexes based on this ligand to obtain new kinds of luminescent Cu(Ⅰ) complexes, and obtained some interesting results:1. Two new binuclear complexes [Cu2 (μ-4,4'-bpy)(phen) 2(PPh3) 2](BF4) 2 (1) and [Cu2 (μ-4,4'-bpy)(2,2'-bpy) 2(PPh3) 2] (BF4) 2 (2) containing 1,10'-phen or 2,2'-bipy and 4,4'-bipy were synthesized and their X-ray structure analysis indicates two copper (I) center of both complexes bridged by 4,4'-bipyridine are center-symmetry geometry. The Cu(Ⅰ) atom adopts distorted tetrahedron geometry, and the distances of copper-copper (11.228 A for 1 and 11.216A for 2) indicate no copper-copper interaction exists. Both complexes have luminescent properties in solid state (λmax(emi) 617 nm 1 and 624 nm 2) and in glass solution (λmax(emi) 562 nm 1 and 580 nm 2), which are attributed to MLCT emission.2. A new eight-member cycle binuclear copper (I) complex [Cu2 (phen) 2(dppm) 2](BF4)2 (3) has been synthesized and characterized. The X-ray structure indicate the center atom adopts distorted tetrahedron geometry and two copper (I) center are bridged by dppm to obtain Cu2P4C2 eight-member cycle structure. The distance of copper and copper is 4.720A. Complex 3 displays strong luminescent properties in solid state. The emission spectrum of λmax (emi) = 525 nm are attributed to MLCT emission. The ESR spectrum indicates that higher valent Cu (Ⅱ) is produced in excited state3. A new one-dimension zigzag polynuclear copper (Ⅰ) complex with formula [Cu (μ-4,4'-bipy)(BF4)] n (4) has been synthesized and characterized. X-ray structure analysis shows that the copper center adopts tetrahedron geometry, and coordinates by two N atoms from acetonitrile and two N atoms from different bridging 4,4'-bipyligand. The complex are bridged by 4,4'-bipy to self-assemble one-dimension zigzag structure.