張一知I-Jy Chang李一宏Yi-Hung Lee2019-09-04不公開2019-09-042009http://etds.lib.ntnu.edu.tw/cgi-bin/gs32/gsweb.cgi?o=dstdcdr&s=id=%22GN0696420222%22.&%22.id.&http://rportal.lib.ntnu.edu.tw:80/handle/20.500.12235/100700　　本研究中合成了一系列錸錯合物，Re(dppz)(CO)3(L) (L = Br, NCS, o-pyCOOH, py, im)，並測量它們在不同極性溶劑下 UV-vis、冷光光譜、生命期、分子振動光譜和氧化還原電位，以了解錯合物在不同環境下相對能階位置。 　　由冷光光譜與生命期可以得知，Re(dppz)(CO)3(py) 和 Re(dppz)(CO)3(im) 所顯現的放光激發態為 3IL，Re(dppz)(CO)3Br、Re(dppz)(CO)3(o-pyCOOH) 與 Re(dppz)(CO)3NCS 的最低能階激發態在低極性溶劑下為 3MLCT(phen)，隨著溶劑極性增加，不能發光的 3MLCT(phz) 比例也逐漸增加，並造成量子產率下降。 　　Re(dppz)(CO)3NCS、Re(dppz)(CO)3Br、Re(dppz)(CO)3(py)、Re(dppz)(CO)3(o-pyCOOH)、和 Re(dppz)(CO)3(im) 氧化電位分別為 1.32、1.47、1.39、1.52 和 1.63 V (vs.SCE)，除了Re(dppz)(CO)3NCS 的氧化電位比 Ru(bpy)2dppz (1.34 V) 低之外，其餘錸錯合物氧化電位皆比 Ru(bpy)2dppz 高，有利於光激發態之氧化反應。　　Five rhenium complexes, Re(dppz)(CO)3(L) (L = Br, NCS, o-pyCOOH, py, im), have been synthesized. UV-vis, emission, lifetime, IR spectra and electrochemistry have been measured in various solvents to understand their photophysical properties. 　　From emission spectra and lifetime analysis, we assign the emissive state of Re(dppz)(CO)3(py) and Re(dppz)(CO)3(im) to the triplet interligand transition state (3IL). The emissive state for Re(dppz)(CO)3Br 、Re(dppz)(CO)3(o-pyCOOH) and Re(dppz)(CO)3NCS are assigned to 3MLCT(phen). The lowest excited-state of these complexes, however, are depends on the solvent`s polarity. At low dielectric constant solvents, the lowest excited-state is mainly 3MLCT(phen), while at high dielectric constant solvent, the non-emissive state of 3MLCT(phz) plays an important part. 　　The oxidation potentials for Re(dppz)(CO)3NCS, Re(dppz)(CO)3Br, Re(dppz)(CO)3(o-pyCOOH), Re(dppz)(CO)3(py) and Re(dppz)(CO)3(im) are 1.32, 1.39, 1.47, 1.52 and 1.63 V (vs.SCE); respectively. Except Re(dppz)(CO)3NCS,all complexes have higher potential than Ru(bpy)2dppz of 1.34 V. Such a high oxidation potential provides these complexes an excellent candidate for photoinduced oxidation reactions.錸Rhenium