Design of diethynyl porphyrin derivatives with high near infrared fluorescence quantum yields

被引:13
作者
Susumu, Kimihiro [1 ]
Therien, Michael J. [2 ]
机构
[1] Univ Penn, Dept Chem, Philadelphia, PA 19104 USA
[2] French Family Sci Ctr, Dept Chem, Durham, NC 27708 USA
关键词
diethynylporphyrin; benzo[c][1,2,5] thiadiazole; near infrared; fluorescence quantum yield; Strickler-Berg; SENSITIZED SOLAR-CELLS; ELECTRON-ACCEPTING MOIETIES; NONLINEAR-OPTICAL RESPONSE; EXCITED-STATE DYNAMICS; EMISSIVE POLYMERSOMES; EPR SPECTROSCOPY; 1ST HYPERPOLARIZABILITY; FREQUENCY DISPERSION; TRIPLET-STATE; CHROMOPHORES;
D O I
10.1142/S1088424614501107
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
A design strategy for (porphinato) zinc-based fluorophores that possess large near infrared fluorescence quantum yields is described. These fluorophores are based on a (5,15-diethynylporphinato) zinc(II) framework and feature symmetric donor or acceptor units appended at the meso-ethynyl positions via benzo[c][1,2,5] thiadiazole moieties. These (5,15-bis(benzo[c][1 ', 2 ', 5 '] thiadiazol-4 '-ylethynyl)-10,20-bis[2 ', 6 '-bis(3 '', 3 ''-dimethyl-1 ''-butyloxy) phenyl] porphinato) zinc(II) (4), (5,15-bis[4 '-(N, N-dihexylamino) benzo[c][1 ', 2 ', 5 '] thiadiazol-7 '-ylethynyl]-10,20-bis[2 ', 6 '-bis(3 '', 3 ''-dimethyl-1.-butyloxy) phenyl] porphinato) zinc(II) (5), (5,15-bis([7 '-(4 ''-n-dodecyloxyphenylethynyl) benzo[c][1 ', 2 ', 5 '] thiadiazol-4 '-yl] ethynyl)-10,20-bis[2 ', 6 '-bis(3 ''., 3 ''-dimethyl-1.-butyloxy) phenyl] porphinato) zinc(II) (6), (5,15-bis([7 '([7 ''-(4 '''-n-dodecyloxyphenyl) benzo[c][1 '', 2 '', 5 ''] thiadiazol-4 ''-yl] ethynyl) benzo[c][1 ', 2 ', 5 '] thiadiazol-4 '-yl] ethynyl)-10,20-bis[2 ', 6 '-bis(3 '', 3 ''-dimethyl-1.-butyloxy) phenyl] porphinato) zinc(II) (7), 5,15-bis ([7 '-(4 ''-N, N-dihexylaminophenylethynyl) benzo[c][1 ', 2 ', 5 '] thiadiazol-4 '-yl] ethynyl)-10,20-bis[2 ', 6 '-bis(3 '', 3 ''-dimethyl-1.-butyloxy) phenyl] porphinato) zinc(II) (8), and (5,15-bis([7 '-(4 ''-N, N-dihexylaminophenylethenyl) benzo[c][1 ', 2 ', 5 '] thiadiazol-4 '-yl] ethynyl)-10,20-bis[2 ', 6 '-bis(3 '', 3 '' dimethyl-1 ''-butyloxy) phenyl] porphinato) zinc(II) (9) chromophores possess red-shifted absorption and emission bands that range between 650 and 750 nm that bear distinct similarities to those of the chlorophylls and structurally related molecules. Interestingly, the measured radiative decay rate constants for these emitters track with the integrated oscillator strengths of their respective x-polarized Q-band absorptions, and thus define an unusual family of high quantum yield near infrared fluorophores in which emission intensity is governed by a simple Strickler-Berg dependence.
引用
收藏
页码:205 / 218
页数:14
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