The Synthesis and Dynamic Structures of Multinuclear Complexes of Large Porphyrinoids Expanded by Phenylene and Thienylene Spacers
The Synthesis and Dynamic Structures of Multinuclear Complexes of Large Porphyrinoids Expanded by Phenylene and Thienylene Spacers
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DOI：
10.1002/chem.201501570
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发表时间：
2015-09-01
影响因子：
4.3
通讯作者：
Watanabe, Keigo
中科院分区：
文献类型：
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作者：
Setsune, Jun-ichiro;Toda, Masayuki;Watanabe, Keigo
以1，3-二(2-吡咯基)苯为原料，用苯取代了[24]-氨甲基(1.0.0.1.0.0)中的两个吡咯单元，合成了二苯并甲氰菊酯。用1，4-二(2-吡咯基)苯、2，5-二(2-吡咯基)噻吩和4，4-二(2-吡咯基)联苯取代2，2-联吡咯，得到[24]罗沙林(1.0.1.0.1.0)和[32]八氢吡喃(1.0.1.0.1.0.1.0)的扩展类似物。X-射线结晶学表明，这些大的卟啉化合物可以结合Rh(CO)(2)和Pd(-烯丙基)的多个金属单元，金属原子与二吡咯平面有相当大的偏离。配位的Rh(CO)(2)基团在大环的两侧穿梭；速度取决于间隔基、环的大小和金属原子的数量。变温-H-1谱表明，由于Rh(CO)(2)基团在大环腔中的跃迁，扩展的玫瑰红素与1，4-亚苯基或2，5-亚硫烯间基团形成的三铑配合物具有C-3v对称性和C-S对称性。C-3v对称型具有较大的偶极矩，因此在极性较大的溶剂中受到青睐。含4，4-联苯基团的膨胀罗沙林三铑配合物中的Rh(CO)(2)基团跃迁如此之快，以至于在-60℃的(H核磁共振)-H-1谱中也能看到平均谱型(D-3h)，即使在-60℃也是如此。具有1，4-亚苯基和2，5-亚硫烯间隔基的膨胀八氢呋喃与大环腔外的四个Rh(CO)(2)基团结合形成D-2d对称的鞍形结构，即使在80℃也不表现出任何动态行为。
1,3-Bis(2-pyrryl)benzene was used to prepare dibenziamethyrin, in which two pyrrole units of [24]amethyrin(1.0.0.1.0.0) are replaced by benzene. 1,4-Bis(2-pyrryl)benzene, 2,5-bis(2-pyrryl)thiophene, and 4,4-bis(2-pyrryl)biphenyl were also used in place of 2,2-bipyrrole to give expanded analogues of [24]rosarin(1.0.1.0.1.0) and [32]octaphyrin(1.0.1.0.1.0.1.0). These large porphyrinoids can incorporate multiple metal units of Rh(CO)(2) and Pd(-allyl) with considerable deviation of the metal atoms from the dipyrrin planes, evidenced by X-ray crystallography. The coordinated Rh(CO)(2) group shuttled between both sides of the macrocycle; the rate was dependent on the spacer, ring size, and number of metal atoms. Variable temperature (HNMR)-H-1 spectroscopy showed that the tris-rhodium complexes of the expanded rosarins with 1,4-phenylene or 2,5-thienylene spacers adopt a C-3v-symmetric form and a C-s-symmetric form as a result of the Rh(CO)(2) groups hopping through the macrocycle cavity. The C-3v-symmetric form has a greater dipole moment and, therefore, is favored in solvents of greater polarity. The Rh(CO)(2) groups in the tris-rhodium complex of the expanded rosarin with 4,4-biphenylene spacers hop so fast that an averaged spectral pattern (D-3h) was seen in the (HNMR)-H-1 spectrum, even at -60 degrees C. Expanded octaphyrins with 1,4-phenylene and 2,5-thienylene spacers bind four Rh(CO)(2) groups outside the macrocycle cavity to form a D-2d-symmetric saddle-shaped structure that did not show any dynamic behavior on the NMR timescale, even at 80 degrees C. This tetranuclear complex is one of the largest porphyrinoid metal complexes characterized by X-ray crystallography to date.