“N-Fused Porphyrin”: A New Tetrapyrrolic Porphyrinoid with a Fused Tri-pentacyclic Ring
“N-Fused Porphyrin”: A New Tetrapyrrolic Porphyrinoid with a Fused Tri-pentacyclic Ring
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DOI：
10.1021/ja000148i
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发表时间：
2000-05
影响因子：
15
通讯作者：
H. Furuta;Tomoya Ishizuka;A. Osuka;T. Ogawa
中科院分区：
文献类型：
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作者：
H. Furuta;Tomoya Ishizuka;A. Osuka;T. Ogawa
介绍了新型卟啉类化合物“N-稠合卟啉(NFP)”的合成、X-射线结构及其反应活性。在室温下，溴代N-混杂的四芳基卟啉在吡啶溶液中自发生成NFP。X-射线衍射分析表明，含有稠合的三五环的类卟啉核心几乎是平面的。例如，与4E‘平均平面的偏差在0.30A以内，外周芳基分别相对于卟啉平均平面倾斜50.4、53.5、64.4和12.4°。通过核磁共振中内NH信号的下场移动(例如，4E‘的8.48ppm)以及内核氮与N2、N3和N4之间的短距离(在2.4−2.9A内)，推测了NFP核中发生了三中心氢键。在CH2Cl2中，NFP的光学吸收光谱在360、500和550 nm附近呈现类Soret跃迁，在650、700、850和940 nm附近有弱的类Q带。并给出了4种不同工艺的电极工艺。
The syntheses and X-ray structures of novel porphyrinoids, “N-fused porphyrins (NFPs)”, and their reactivity were described. NFP was spontaneously produced from the bromo-substituted N-confused tetraarylporphyrin in a pyridine solution at room temperature. X-ray diffraction analyses revealed that the porphyrinoid core containing a fused tri-pentacyclic ring is almost planar. The deviation from the mean plane of 4e‘, for example, was within 0.30 A. The peripheral aryl substituents were tilted 50.4, 53.5, 64.4, and 12.4° relative to the porphyrin mean plane, respectively. The occurrence of a three-centered hydrogen bonding in the NFP core was inferred by the downfield shift of the inner NH signal (e.g., 8.48 ppm for 4e‘) in 1H NMR and the short distances (within 2.4−2.9 A) among the inner core nitrogens, N2, N3, and N4. The optical absorption spectra of NFPs exhibit Soret-like transitions around 360, 500, and 550 nm and weak Q-like bands around 650, 700, 850, and 940 nm in CH2Cl2. The electrode process of 4...