Labra-Vázquez Pablo, Bocé Mathilde, Tassé Marine, Mallet-Ladeira Sonia, Lacroix Pascal G, Farfán Norberto, Malfant Isabelle
Laboratoire de Chimie de Coordination du CNRS, 205 route de Narbonne, F-31077, Toulouse, France.
Dalton Trans. 2020 Mar 14;49(10):3138-3154. doi: 10.1039/c9dt04832d. Epub 2020 Feb 20.
The synthesis and behavior in water of a set of various cis(Cl,Cl)-R-tpyRuCl(NO) and trans(Cl,Cl)-R-tpyRuCl(NO) (R = fluorenyl, phenyl, thiophenyl; tpy = 2,2':6',2''-terpyridine) complexes are presented. In any case, one chlorido ligand is substituted by a hydroxo ligand and the final species arises as a single trans(NO,OH) isomer, whatever the nature of the starting cis/trans(Cl,Cl) complexes. Six X-ray crystal structures are presented for cis(Cl,Cl)-thiophenyl-tpyRuCl(NO) (cis-3a), trans(Cl,Cl)-thiophenyl-tpyRuCl(NO) (trans-3a), trans(NO,OH)-phenyl-tpyRu(Cl)(OH)(NO) (4a), trans(NO,OH)-thiophenyl-tpyRu(Cl)(OH)(NO) (4b), trans(NO,OEt)-phenyl-tpyRu(Cl)(OEt)(NO) (5a), and trans(NO,OH)-phenyl-tpyRu(Cl)(OEt)(NO) (5b) compounds. The different cis/trans(Cl,Cl) complexes exhibit an intense low-lying transition in the λ = 330-390 nm range, which appears to be slightly blue-shifted after Cl → OH substitution. In water, both cis/trans(Cl,Cl) isomers are converted to a single trans(NO,OH) isomer in which one chlorido- is replaced by one hydroxo-ligand, which avoids tedious separation workout. The water stable trans(NO,OH)-species all release NO with quantum yields of 0.010 to 0.075 under irradiation at 365 nm. The properties are discussed with computational analysis performed within the framework of Density Functional Theory.
本文介绍了一系列顺式(Cl,Cl)-R-三联吡啶钌氯(NO)和反式(Cl,Cl)-R-三联吡啶钌氯(NO)（R = 芴基、苯基、噻吩基；tpy = 2,2':6',2''-三联吡啶）配合物在水中的合成及行为。在任何情况下，无论起始顺式/反式(Cl,Cl)配合物的性质如何，一个氯配体都会被一个羟基配体取代，最终产物以单一的反式(NO,OH)异构体形式出现。文中给出了顺式(Cl,Cl)-噻吩基-三联吡啶钌氯(NO)（顺式-3a）、反式(Cl,Cl)-噻吩基-三联吡啶钌氯(NO)（反式-3a）、反式(NO,OH)-苯基-三联吡啶钌(Cl)(OH)(NO)（4a）、反式(NO,OH)-噻吩基-三联吡啶钌(Cl)(OH)(NO)（4b）、反式(NO,OEt)-苯基-三联吡啶钌(Cl)(OEt)(NO)（5a）和反式(NO,OH)-苯基-三联吡啶钌(Cl)(OEt)(NO)（5b）化合物的六个X射线晶体结构。不同的顺式/反式(Cl,Cl)配合物在λ = 330 - 390 nm范围内呈现出强烈的低能跃迁，在Cl → OH取代后似乎略有蓝移。在水中，顺式/反式(Cl,Cl)异构体均转化为单一的反式(NO,OH)异构体，其中一个氯配体被一个羟基配体取代，这避免了繁琐的分离操作。水稳定的反式(NO,OH)物种在365 nm光照下均以0.010至0.075的量子产率释放NO。文中结合密度泛函理论框架下进行的计算分析对这些性质进行了讨论。
