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首页> 外文期刊>Chemistry: A European journal >Tandem Cofacial Stacks of PorphyrinCPhthalocyanine Dyads through Complementary Coordination
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Tandem Cofacial Stacks of PorphyrinCPhthalocyanine Dyads through Complementary Coordination

机译：通过互补配位的卟啉CP酞菁二联成排的串联堆栈。

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摘要

A novel straightforward methodology to organize discrete heterogeneous stacks of porphyrin and phthalocyanine employed an imidazolyl-to-zinc complementary coordination protocol for a ZnII phthalocyanine that contains an imidazolyl terminal with an ethynylporphyrin as a coplanar spacer. Structural elucidation was performed by means of size-exclusion chromatography, spectral titration, and NMR spectroscopy. The association constants for the complementary coordination of the heterogeneous slipped-cofacial tetrads reached extremely high values, in the order of 1014m-1. Close contact of the porphyrin and phthalocyanine planes led to a strong shielding of the cofacial protons, which were split due to the slipped-cofacial heterogeneous environment. In variable-temperature NMR spectroscopy, the split signals remained in the aromatic region, a result suggesting structural robustness. Addition of trifluoroacetic acid dissociated the coordination structure to unify the split signals. The stacked tetrads showed unique electronic structures, such as strong exciton coupling and charge-transfer properties between the porphyrin and phthalocyanine units, which were modulated by the peripheral substituents of the phthalocyanine subunit and by the solvent. Interconversion between the coordination tetrad and the corresponding dyad was observed upon addition of an axial ligand.
机译：一种新颖简单的方法来组织卟啉和酞菁的不均匀异质堆叠，对ZnII酞菁使用咪唑基与锌的互补配位方案，该协议包含一个咪唑基末端与乙炔基卟啉作为共面的间隔基。通过尺寸排阻色谱法，光谱滴定法和NMR光谱法进行结构阐明。异质滑面四面体的互补配位的缔合常数达到极高的值，约为1014m-1。卟啉和酞菁平面的紧密接触导致对界面质子的强烈屏蔽，由于界面不均匀的不均匀环境，界面质子分裂。在变温NMR光谱中，分离的信号保留在芳族区域中，结果表明结构坚固。三氟乙酸的加入解离了配位结构以统一分裂信号。堆积的四线联体显示出独特的电子结构，例如卟啉和酞菁单元之间的强激子耦合和电荷转移性质，这些性质由酞菁亚基的周边取代基和溶剂调节。加入轴向配体后，观察到配位四元体与相应二元体之间的相互转化。

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