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首页> 外文期刊>Chemistry: A European journal >Tribenzotriquinacene Receptors for C_(60) Fullerene Rotors: Towards C_3 Symmetrical Chiral Stators for Unidirectionally Operating Nanoratchets
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Tribenzotriquinacene Receptors for C_(60) Fullerene Rotors: Towards C_3 Symmetrical Chiral Stators for Unidirectionally Operating Nanoratchets

机译：C_（60）富勒烯转子的三苯并三喹并二苯受体：单向操作纳米棘轮的C_3对称手性定子。

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The synthesis of a stereochemically pure concave tribenzotriquinacene receptor (7) for C_(60) fullerene, possessing C_3 point group symmetry, by threefold condensation of C_2-symmetric 1,2-diketone synthons (5) and a hexaaminotribenzotriquinacene core (6) is described. The chiral diketone was synthesized in a five-step reaction sequence starting from C_(2h)-symmetric 2,6-di-tert-butylanthracene. The highly diastereo-discriminating Diels-Alder reaction of 2,6-di-tertbutylanthracene with fumaric acid di(-)menthyl ester, catalyzed by aluminium chloride, is the relevant stereochemistry introducing step. The structure of the fullerene receptor was verified by ~1H and ~(13)C NMR spectroscopy, mass spectrometry and single crystal X-ray diffraction. VCD and ECD spectra were recorded, which were corroborated by ab initio DFT calculations, establishing the chiral nature of 7 with about 99.7% ee, based on the ee (99.9%) of the chiral synthon (1). The absolute configuration of 7 could thus be established as all-S [(2S,7S,16S,21S,30S,35S)-(7)] . Spectroscopic titration experiments reveal that the host forms 1:1 complexes with either pure fullerene (C_(60)) or fullerene derivatives, such as rotor 1'-(4-nitrophenyl)-3'-(4-N,N-dimethylaminophenyl)-pyrazolino[ 4',5':1,2][60]fullerene (R). The complex stability constants of the complexes dissolved in CHCl_3/CS_2 (1:1 vol.%) are K([C_(60)?7])=319(±156)M~(-1) and K([R?7])=110(±50)M~(-1). With molecular dynamics simulations using a first-principles parameterized force field the asymmetry of the rotational potential for [R?7] was shown, demonstrating the potential suitability of receptor 7 to act as a stator in a unidirectionally operating nanoratchet.
机译：描述了通过C_2对称的1,2-二酮合成子（5）和六氨基三苯并三喹烯核（6）的三重缩合合成具有C_3点基对称性的C_（60）富勒烯的立体化学纯凹型三苯并三喹并苯受体（7）。 。从C_（2h）-对称的2,6-二叔丁基蒽开始，按五步反应顺序合成了手性二酮。相关的立体化学引入步骤是2,6-二叔丁基蒽与富马酸二（-）薄荷酯的高度非对映异构的Diels-Alder反应。富勒烯受体的结构通过〜1H和〜（13）C NMR光谱，质谱和单晶X射线衍射验证。记录了VCD和ECD光谱，这些光谱通过从头算DFT计算得到证实，基于手性合成子（1）的ee（99.9％），确定了7的手性，其中ee约为99.7％。因此，可以将7的绝对配置确定为all- [[（2S，7S，16S，21S，30S，35S）-（7）]。光谱滴定实验表明，主体与纯富勒烯（C_（60））或富勒烯衍生物，例如转子1'-（4-硝基苯基）-3'-（4-N，N-二甲基氨基苯基）形成1：1配合物-吡唑啉代[4'，5'：1,2] [60]富勒烯（R）。溶解于CHCl_3 / CS_2（1：1体积％）的配合物的配合物稳定常数为K（[C_（60）？7]）= 319（±156）M〜（-1）和K（[R？ 7]）= 110（±50）M〜（-1）。通过使用第一性原理参数化力场的分子动力学模拟，显示了[R？7]旋转电位的不对称性，证明了受体7在单向操作纳米棘轮中作为定子的潜在适用性。

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