Synthesis and spectroelectrochemistry of N-cobaltacarborane porphyrin conjugates.
Synthesis and spectroelectrochemistry of N-cobaltacarborane porphyrin conjugates.
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DOI：
10.1021/bc800265w
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发表时间：
2008-11-19
影响因子：
4.7
通讯作者：
Vicente, M. Graca H.
中科院分区：
文献类型：
--
作者：
Hao, Erhong;Zhang, Min;E, Wenbo;Kadish, Karl M.;Fronczek, Frank R.;Courtney, Brandy H.;Vicente, M. Graca H.
众所周知，N-取代的卟啉通过吡咯单元之一的sp3杂化而表现出卟啉平面的畸变。它们在许多生物化学过程的研究中被用作模型化合物。在本文中，我们开发了一种有效的N-取代卟啉的路线，并报道了一系列新的N-取代的钴硼烷卟啉含有一个或两个钴双碳环阴离子连接的（CH_2CH_2 O）_2链的核心卟啉氮或meso-aminophenyl。这些共轭物显示出不同程度的卟啉大环的畸变，这影响了它们的光谱和电化学性质。特别地，与非核心取代的大环相比，核心N-取代的缀合物显示出显著的荧光猝灭。本文报道了两种靶向核N-钴碳硼烷卟啉共轭物的X-射线结构。这些卟啉共轭物的电化学和光谱电化学性能进行了研究，而外围的N-取代的钴碳硼烷卟啉经历三个可逆的还原和三个可逆的氧化（两个归因于卟啉和一个的CoIII簇），核心的N-取代的卟啉表现出复杂的电化学行为与耦合的化学反应。
N-Substituted porphyrins are well known for the distortion they exhibit of the porphyrin plane through the sp3 hybridization of one of the pyrrolenic units. They have served as model compounds in investigations of many biochemical processes. In this paper, we developed an efficient route to N-substituted porphyrins, and report the synthesis of a series of new N-substituted cobaltacarborane-porphyrins containing one or two cobaltabisdicarbollide anions linked by (CH2CH2O)2 chains to either the core porphyrin nitrogens or to a meso-aminophenyl group. These conjugates show different degrees of distortion of the porphyrin macrocycle, which affect their spectroscopic and electrochemical properties. In particular, the core N-substituted conjugates show significant fluorescence quenching in comparison with the non-core substituted macrocycles. The X-ray structures of two targeted core N-cobaltacarborane porphyrin conjugates are presented. The electrochemical and spectroelectrochemical properties of these porphyrin conjugates were investigated; while the peripheral N-substituted cobaltacarboranylporphyrins undergo three reversible reductions and three reversible oxidations (two attributed to the porphyrin and one to the CoIII cluster), the core N-substituted porphyrins exhibit complicated electrochemical behavior with coupled chemical reactions.
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影响因子：
4.3
作者：
Hao, Erhong;Sibrian-Vazquez, Martha;Vicente, M. Graca H.
通讯作者：
Vicente, M. Graca H.
影响因子：
15
作者：
KONISHI, K;YAHARA, K;INOUE, S
通讯作者：
INOUE, S
影响因子：
4.6
作者：
MALINSKI, T;CHANG, D;KADISH, KM
通讯作者：
KADISH, KM
影响因子：
4.6
作者：
BETTELHEIM, A;WHITE, BA;MURRAY, RW
通讯作者：
MURRAY, RW
影响因子：
4.9
作者：
Hao, E;Vicente, MGH
通讯作者：
Vicente, MGH