Phenothiazine-Bridged Cyclic Porphyrin Dimers as High-Affinity Hosts for Fullerenes and Linear Array of C60 in Self-Assembled Porphyrin Nanotube

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• 作者：Ken-ichi Sakaguchi ; Takuya Kamimura ; Hidemitsu Uno ; Shigeki Mori ; Shuwa Ozako ; Hirofumi Nobukuni ; Masatoshi Ishida ; Fumito Tani
• 刊名：Journal of Organic Chemistry
• 出版年：2014
• 出版时间：April 4, 2014
• 年：2014
• 卷：79
• 期：7
• 页码：2980-2992
• 全文大小：623K
• 年卷期：v.79,no.7(April 4, 2014)
• ISSN：1520-6904

文摘

Free-bases and a nickel(II) complex of phenothiazine-bridged cyclic porphyrin dimers bearing self-assembling 4-pyridyl groups (M₂-Ptz-CPD_Py(OC_n); M = H₂ or Ni, OC_n = OC₆ or OC₃) at opposite meso-positions have been prepared as host molecules for fullerenes. The free-base dimer (H₄-Ptz-CPD_Py(OC₆)) includes fullerenes with remarkably high association constants such as 3.9 卤 0.7 脳 10⁶ M^鈥? for C₆₀ and 7.4 卤 0.8 脳 10⁷ M^鈥? for C₇₀ in toluene. This C₆₀ affinity is the highest value ever among reported receptors composed of free-base porphyrins. The nickel dimer (Ni₂-Ptz-CPD_Py(OC₆)) also shows high affinities for C₆₀ (1.3 卤 0.2 脳 10⁶ M^鈥?) and C₇₀ (over 10⁷ M^鈥?). In the crystal structure of the inclusion complex of C₆₀ within H₄-Ptz-CPD_py(OC₃), the C₆₀ molecule is located just above the centers of the porphyrins. The two porphyrin planes are almost parallel to each other and the center-to-center distance (12.454 脜) is close to the optimal separation (12.5 脜) for C₆₀ inclusion. The cyclic porphyrin dimer forms a nanotube through its self-assembly induced by C鈥揌路路路N hydrogen bonds between porphyrin 尾-CH groups and pyridyl nitrogens as well as 蟺鈥撓€ interactions of the pyridyl groups. The C₆₀ molecules are linearly arranged in the inner channel of this nanotube.