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首页> 外文期刊>Chemistry: A European journal >Synthesis, Aromaticity and Photophysical Behaviour of Ferrocene- and Ruthenocene-Appended Semisynthetic Chlorin Derivatives
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Synthesis, Aromaticity and Photophysical Behaviour of Ferrocene- and Ruthenocene-Appended Semisynthetic Chlorin Derivatives

机译：二茂铁和钌茂金属附加的半合成氯代衍生物的合成，芳香性和光物理行为

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摘要

Two novel synthetic strategies to covalently link a metallocene electron-donor unit to a chlorin ring are presented. In one approach, pyropheophorbidea is readily converted into its 13(1)-ferrocenyl dehydro derivative by nucleophilic addition of the ferrocenyl anion to the 13(1)-carbonyl group. In another approach, the corresponding 13(1)-pentamethylruthenocenyl derivative is synthesised from 13(1)-fulvenylchlorin by a facile ligand exchange/deprotonation reaction with the [RuCp*(cod)Cl] (Cp*=pentamethylcyclopentadienyl; cod=1,5-cyclooctadiene) complex. The resulting metallocene-chlorins exhibit reduced aromaticity, which was unequivocally supported by ring-current calculations based on the gauge-including magnetically induced current (GIMIC) method and by calculated nucleus-independent chemical shift (NICS) values. The negative ring current in the isocyclic E ring suggests the antiaromatic character of this moiety and also clarifies the spontaneous reactivity of the complexes with oxygen. The oxidation products were isolated and their electrochemical and photophysical properties were studied. The ruthenocene derivatives turned out to be stable under light irradiation and showed photoinduced charge transfer with charge-separation lifetimes of 152-1029ps.
机译：提出了两种将金属茂电子供体单元与二氢卟吩环共价连接的新合成策略。在一种方法中，通过将二茂铁基阴离子亲核加成到13（1）-羰基上，发火菌比很容易转化为其13（1）-二茂铁基脱氢衍生物。在另一种方法中，通过与[RuCp *（cod）Cl]的容易的配体交换/去质子化反应，由13（1）-富烯基二氯合成相应的13（1）-五甲基钌烯基衍生物（Cp * =五甲基环戊二烯基; cod = 1， 5-环辛二烯）复合物。所得的茂金属-二氢卟酚显示出降低的芳香性，这是基于基于包括磁感应电流计（GIMIC）的量规的环电流计算和与核无关的化学位移（NICS）的计算值明确支持的。杂环E环中的负环电流表明该部分具有抗芳香特性，并且还阐明了配合物与氧的自发反应性。分离出氧化产物并研究其电化学和光物理性质。钌茂茂衍生物在光照射下证明是稳定的，并显示出光致电荷转移，电荷分离寿命为152-1029ps。

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