Lo Kenneth Kam-Wing, Zhang Kenneth Yin, Chung Chi-Keung, Kwok Karen Ying
Department of Biology and Chemistry, City University of Hong Kong, Tat Chee Avenue, Kowloon, Hong Kong, People's Republic of China.
Chemistry. 2007;13(25):7110-20. doi: 10.1002/chem.200700530.
A new series of luminescent cyclometalated iridium(III) bipyridine estradiol conjugates Ir(N-C)2(N-N) (N-N = 5-(4-(17alpha-ethynylestradiolyl)phenyl)-2,2'-bipyridine, bpy-est, HN-C = 2-phenylpyridine, Hppy (1 a), 1-phenylpyrazole, Hppz (2 a), 7,8-benzoquinoline, Hbzq (3 a), 2-phenylquinoline, Hpq (4 a), 2-((1,1'-biphenyl)-4-yl)benzothiazole, Hbsb (5 a); N-N = 4-(N-(6-(4-(17alpha-ethynylestradiolyl)benzoylamino)hexyl)aminocarbonyl)-4'-methyl-2,2'-bipyridine, bpy-C6-est, HN-C = Hppy (1 b), Hppz (2 b), Hbzq (3 b), Hpq (4 b), Hbsb (5 b)) was synthesized, characterized, and their photophysical and electrochemical properties studied. Upon photoexcitation, all the complexes displayed intense and long-lived emission in fluid solutions at 298 K and in low-temperature glass. The emission of complexes 1 a-3 a and 1 b-3 b was assigned to a triplet metal-to-ligand charge-transfer ((3)MLCT) (dpi(Ir)-->pi*(bpy-est and N-C-)) state mixed with some triplet intraligand ((3)IL) (pi-->pi*) (N-C- and N-N) character. However, the emissive states of the pq- and bsb- complexes 4 a, 4 b, 5 a, and 5 b showed substantial (3)IL (pi-->pi*) (pq-/bsb-) character. The lipophilicity of all the complexes was determined by reversed-phase HPLC. Upon binding to estrogen receptor alpha, all of these iridium(III) estradiol conjugates exhibited emission enhancement and lifetime extension, rendering them a novel series of luminescent probes for this receptor.
合成并表征了一系列新的环金属化铱（III）联吡啶雌二醇共轭物Ir（N-C）2（N-N）（N-N = 5-(4-(17α-乙炔基雌二醇基)phenyl)-2,2'-联吡啶，bpy-est，HN-C = 2-苯基吡啶，Hppy (1 a)，1-苯基吡唑，Hppz (2 a)，7,8-苯并喹啉，Hbzq (3 a)，2-苯基喹啉，Hpq (4 a)，2-((1,1'-联苯)-4-基)苯并噻唑，Hbsb (5 a)；N-N = 4-(N-(6-(4-(17α-乙炔基雌二醇基)苯甲酰氨基)己基)氨基羰基)-4'-甲基-2,2'-联吡啶，bpy-C6-est，HN-C = Hppy (1 b)，Hppz (2 b)，Hbzq (3 b)，Hpq (4 b)，Hbsb (5 b)），并研究了它们的光物理和电化学性质。光激发后，所有配合物在298 K的流体溶液和低温玻璃中均表现出强烈且长寿命的发射。配合物1 a - 3 a和1 b - 3 b的发射归因于三重态金属到配体的电荷转移((3)MLCT)（dpi(Ir)-->pi*(bpy-est和N-C-))态与一些三重态配体内((3)IL)（pi-->pi*)（N-C-和N-N）特征的混合。然而，pq-和bsb-配合物4 a、4 b、5 a和5 b的发射态显示出大量的(3)IL（pi-->pi*)（pq-/bsb-）特征。通过反相高效液相色谱法测定了所有配合物的亲脂性。与雌激素受体α结合后，所有这些铱（III）雌二醇共轭物均表现出发射增强和寿命延长，使其成为该受体的一系列新型发光探针。
