Synthesis, characterization and electrochemistry of rhodium(III) complexes of meso-substituted [14]tribenzotriphyrin(2.1.1)

Xue Zhaoli; Wang Yemei; Mack John; Mkhize Scebi; Nyokong Tebello; Fang Yuanyuan; Ou Zhongping; Kadish Karl M.

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Synthesis, characterization and electrochemistry of rhodium(III) complexes of meso-substituted [14]tribenzotriphyrin(2.1.1)

机译：中甲醛（III）复合物的合成，表征和电化学络合物[14]呋喃酚萘嘧啶（2.1.1）

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A thermal reaction using a series of [14]tribenzotriphyrins(2.1.1) (TriPs, 1a-d) with Rh-2(C8H12)Cl-2 provides Rh-III-TriP complexes (2a-d) in 40-52% yields. The complexes were characterized by mass spectrometry, UV-visible absorption and H-1 NMR spectroscopy. Single crystal X-ray analysis reveals that 2b adopts a dome-shaped conformation. The rhodium(III) ion is coordinated by the three pyrrole nitrogen atoms, two chloride ions and the nitrogen atom of an acetonitrile (CH3CN) solvent molecule. The optical spectra can be assigned using Michl's perimeter model. The L and B bands of the 2a-d complexes lie at ca. 600 and 500 nm, respectively, and are markedly red shifted relative to those of 1a-d. A reversible one-electron oxidation and two reversible one-electron reductions are observed in the cyclic voltammograms of 2a-d in CH2Cl2. The redox potentials are consistent with the optical data and the relatively narrow HOMO-LUMO gaps that are predicted in DFT calculations. TD-DFT calculations have been used to assign a third intense spectral band at 375 nm to a higher energy pi -> pi* transition of the [14]tribenzotriphyrin(2.1.1) pi-system.

机译：使用RH-2（C8H12）Cl-2的一系列[14]呋喃酚苯吡嗪（2.1.1）（TRIPS，1A-D）的热反应提供RH-III跳闸配合物（2A-D），在40-52％中提供产量。通过质谱，UV可见吸收和H-1 NMR光谱表征复合物的特征。单晶X射线分析显示，2B采用圆顶形构象。铑（III）离子由三个吡咯氮原子，两种氯离子和乙腈（CH3CN）溶剂分子的氮原子配位。可以使用MICHL的周边模型分配光谱。 2A-D复合物的L和B带位于CA.分别为600和500nm，并且相对于1A-D的那些，显着的红色移位。在CH 2 Cl 2中的循环伏安图中，在2A-D的循环伏安图中观察到可逆的单电子氧化和两个可逆的单电子减少。氧化还原电位与光学数据和在DFT计算中预测的相对窄的同性恋间隙一致。已经使用TD-DFT计算在375nm处将第三激谱带分配给更高的能量Pi - > Pi * [14]呋喃啉吡啶（2.1.1）pi-system的转变。

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《RSC Advances》 |2016年第48期|共8页
作者
Xue Zhaoli; Wang Yemei; Mack John; Mkhize Scebi; Nyokong Tebello; Fang Yuanyuan; Ou Zhongping; Kadish Karl M.;
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Jiangsu Univ Sch Chem &

Chem Engn Zhenjiang 212013 Peoples R China;

Jiangsu Univ Sch Chem &

Chem Engn Zhenjiang 212013 Peoples R China;

Rhodes Univ Dept Chem POB 94 ZA-6140 Grahamstown South Africa;

Rhodes Univ Dept Chem POB 94 ZA-6140 Grahamstown South Africa;

Rhodes Univ Dept Chem POB 94 ZA-6140 Grahamstown South Africa;

Jiangsu Univ Sch Chem &

Chem Engn Zhenjiang 212013 Peoples R China;

Jiangsu Univ Sch Chem &

Chem Engn Zhenjiang 212013 Peoples R China;

Univ Houston Dept Chem Houston TX 77204 USA;

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1. Synthesis, characterization and electrochemistry of rhodium(III) complexes of meso-substituted [14]tribenzotriphyrin(2.1.1) [J] . Xue Zhaoli, Wang Yemei, Mack John, RSC Advances . 2016,第48期

机译：中甲醛（III）复合物的合成，表征和电化学络合物[14]呋喃酚萘嘧啶（2.1.1）
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Synthesis, characterization and electrochemistry of rhodium(III) complexes of meso-substituted [14]tribenzotriphyrin(2.1.1)

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