β,β-Directly Linked Porphyrin Rings: Synthesis, Photophysical Properties, and Fullerene Binding.
β,β-Directly Linked Porphyrin Rings: Synthesis, Photophysical Properties, and Fullerene Binding.
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DOI：
10.1021/jacs.3c03549
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发表时间：
2023-05-31
影响因子：
15
通讯作者：
Anderson, Harry L.
中科院分区：
文献类型：
--
作者：
Chen, Qiang;Thompson, Amber L.;Christensen, Kirsten E.;Horton, Peter N.;Coles, Simon J.;Anderson, Harry L.
环卟啉低聚物已被研究作为光合作用光收集天线复合物的模型和潜在的超分子化学受体。在这里，我们报道了前所未有的β，β-直接连接的环锌卟啉低聚物，三聚体（CP3）和四聚体（CP4），通过山本偶联2,3-二溴卟啉前体。它们的三维结构被核磁共振（NMR）光谱、质谱和单晶x射线衍射分析证实。根据密度泛函理论计算，CP3和CP4的最小能量几何形状分别为螺旋桨和鞍形。它们不同的几何形状导致了不同的光物理和电化学性质。与CP4相比，CP3中卟啉单元之间的二面角较小，导致π共轭作用更强，使紫外-可见吸收带分裂并向更长的波长移动。晶体键长分析表明，CP3的中心苯环是部分芳香的[芳香性谐振子模型（HOMA） 0.52]，而CP4的中心环四烯环是非芳香的（HOMA -0.02）。CP4的鞍形结构使其成为富勒烯的双位受体，在298 K甲苯溶液中对C70和C60的亲和常数分别为（1.1±0.4）× 105 M-1和（2.2±0.1）× 104 M-1。通过核磁共振滴定和x射线单晶衍射证实了与C60形成1:2的配合物。
Cyclic porphyrin oligomers have been studied as models for photosynthetic light-harvesting antenna complexes and as potential receptors for supramolecular chemistry. Here, we report the synthesis of unprecedented β,β-directly linked cyclic zinc porphyrin oligomers, the trimer (CP3) and tetramer (CP4), by Yamamoto coupling of a 2,3-dibromoporphyrin precursor. Their three-dimensional structures were confirmed by nuclear magnetic resonance (NMR) spectroscopy, mass spectrometry, and single-crystal X-ray diffraction analyses. The minimum-energy geometries of CP3 and CP4 have propeller and saddle shapes, respectively, as calculated using density functional theory. Their different geometries result in distinct photophysical and electrochemical properties. The smaller dihedral angles between the porphyrin units in CP3, compared with CP4, result in stronger π-conjugation, splitting the ultraviolet–vis absorption bands and shifting them to longer wavelengths. Analysis of the crystallographic bond lengths indicates that the central benzene ring of the CP3 is partially aromatic [harmonic oscillator model of aromaticity (HOMA) 0.52], whereas the central cyclooctatetraene ring of the CP4 is non-aromatic (HOMA –0.02). The saddle-shaped structure of CP4 makes it a ditopic receptor for fullerenes, with affinity constants of (1.1 ± 0.4) × 105 M–1 for C70 and (2.2 ± 0.1) × 104 M–1 for C60, respectively, in toluene solution at 298 K. The formation of a 1:2 complex with C60 is confirmed by NMR titration and single-crystal X-ray diffraction.
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影响因子：
15
作者：
Hogben, Hannah J.;Sprafke, Johannes K.;Anderson, Harry L.
通讯作者：
Anderson, Harry L.
影响因子：
15
作者：
KAGAN, NE;MAUZERALL, D;MERRIFIELD, RB
通讯作者：
MERRIFIELD, RB
DOI：
10.1039/c39890001714
发表时间：
1989-11-15
影响因子：
--
作者：
ANDERSON, HL;SANDERS, JKM
通讯作者：
SANDERS, JKM
影响因子：
5.2
作者：
Gil-Ramirez, Guzman;Karlen, Steven D.;Anderson, Harry L.
通讯作者：
Anderson, Harry L.
影响因子：
5.2
作者：
Gryko, DT;Galezowski, M
通讯作者：
Galezowski, M