Synthesis and properties of hybrid porphyrin tapes.
Synthesis and properties of hybrid porphyrin tapes.
复制标题
杂化卟啉带的合成及性能。
作者：
Takayuki Tanaka;Byung Sun Lee;N. Aratani;Min;Dongho Kim;A. Osuka
由3，5-二叔丁基苯基取代的供体型锌(II)-卟啉和五氟苯基取代的受体型锌(II)-卟啉通过镍(II)-卟啉和五氟苯基-二吡咯甲烷与五氟苯甲醛的交叉缩合反应，然后进行适当的脱金属化、再金属化和氧化闭环反应，合成了杂化卟啉带3和4。用类似的方法制备了Ni(II)取代的5(Ni-Zn-Ni)和6(Ni-H(2)-Ni)。杂化卟啉带3和4比正常的只含给体型锌(II)-卟啉的卟啉带1和2更易溶解和更稳定。通过单晶X射线衍射分析，确定了化合物3、4和5的固体堆积结构和晶体堆积结构。单个介观-介观连接的杂化卟啉阵列12和14表现出大致对应于每个组成的卟啉片段的氧化还原电位，而杂化卟啉带3和4的氧化还原电位作为一个整体正移。用波长扫描Z-扫描法测量了1-6的双光子吸收，分别为1900，21,000,2200，27,000，24,000和26,000 GM。这些结果说明了延长π-电子共轭对提高TPA值的重要作用。杂交型卟啉胶带的TPA值略大于亲本。
Hybrid porphyrin tapes 3 and 4, consisting of a mixture of 3,5-di-tert-butylphenyl-substituted donor-type Zn(II)-porphyrins and pentafluorophenyl-substituted acceptor-type Zn(II)-porphyrins, were prepared by a synthetic route involving cross-condensation reaction of a Ni(II)-porphyrinyldipyrromethane and pentafluorophenyldipyrromethane with pentafluorobenzaldehyde followed by appropriate demetalation, remetalation, and oxidative ring-closure reaction. The Ni(II)-substituted porphyrin tapes 5 (Ni-Zn-Ni) and 6 (Ni-H(2)-Ni) were also prepared through similar routes. The hybrid porphyrin tapes 3 and 4 are more soluble and more stable than normal porphyrin tapes 1 and 2 consisting of only donor-type Zn(II)-porphyrins. The solid-state and crystal packing structures of 3, 4, and 5 were elucidated by single-crystal X-ray diffraction analysis. Singly meso-meso-linked hybrid porphyrin arrays 12 and 14 exhibit redox potentials that roughly correspond to each constituent porphyrin segments, while the redox potentials of the hybrid porphyrin tapes 3 and 4 are positively shifted as a whole. The two-photon absorption (TPA) values of 1-6 were measured by using a wavelength-scanning open aperture Z-scan method and found to be 1900, 21,000, 2200, 27,000, 24,000, and 26,000 GM, respectively. These results illustrate an important effect of elongation of π-electron conjugation for the enhancement of TPA values. The hybrid porphyrin tapes show slightly larger TPA values than the parent ones.
影响因子：
15
作者：
Davis, Nicola K. S.;Thompson, Amber L.;Anderson, Harry L.
通讯作者：
Anderson, Harry L.
影响因子：
56.9
作者：
LIN, VSY;DIMAGNO, SG;THERIEN, MJ
通讯作者：
THERIEN, MJ