Cyclic 2,12-Porphyrinylene Nanorings as a Porphyrin Analogue of Cycloparaphenylenes
Cyclic 2,12-Porphyrinylene Nanorings as a Porphyrin Analogue of Cycloparaphenylenes
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DOI：
10.1021/ja513102m
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发表时间：
2015-02-18
影响因子：
15
通讯作者：
Osuka, Atsuhiro
中科院分区：
文献类型：
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作者：
Jiang, Hua-Wei;Tanaka, Takayuki;Osuka, Atsuhiro
通过2，12-二硼化镍(II)与铂(CoD)Cl2反应，还原消除，合成了直接连接的环状镍(II)三聚体、四聚体和五聚体([3]CP、[4]Cp和[5]Cp)。通过X-射线衍射分析，确定了这些环状卟啉阵列的结构。对[3]Cp、[4]Cp和[5]Cp，这些环状低聚物的应变能分别为77、57和47kcal/mol。在Ni(II)的(3)(d，d)态之间观察到分子内激发能跃迁，[3]Cp，[4]Cp和[5]Cp的激发速率分别为3.0，4.4和4.6ps，反映了Ni(II)中心的接近。
beta-to-beta Directly linked cyclic Ni(II) porphyrin trimer, tetramer, and pentamer ([3]CP, [4]CP, and [5]CP) have been synthesized by reaction of a 2,12-diborylated Ni(II) porphyrin with Pt(cod)Cl-2 followed by reductive elimination. The structures of these cyclic porphyrin arrays have been revealed by X-ray diffraction analysis. The strain energies of these cyclic oligomers are calculated to be 77, 57, and 47 kcal/mol for [3]CP, [4]CP, and [5]CP, respectively. Intramolecular excitation energy hopping was observed between the (3)(d,d) states of the Ni(II) porphyrins with rates of 3.0, 4.4, and 4.6 ps for [3]CP, [4]CP, and [5]CP, respectively, reflecting the close proximity of the Ni(II) centers.