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Investigating the Photochemistry of Spiropyran Metal Complexes with Online LED-NMR
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2019-10-26 , DOI: 10.1021/acs.inorgchem.9b02547
Thomas J. Feuerstein 1 , Rouven Müller 2 , Christopher Barner-Kowollik 2, 3 , Peter W. Roesky 1
Affiliation  

As one of the best studied photoswitches, spiropyrans (SPs) have attracted significant interest in the scientific community. Among the many stimuli to alter the isomerization into the merocyanine (MC) isomer, such as temperature, pH, solvent polarity, redox potential, or mechanical force, the ability of the MC form to act as a ligand site for metal complexation has recently raised new attention. We herein synthesize hitherto undescribed coordination compounds of 8-methoxy-1′,3′,3′-trimethyl-6-nitrospiro-[chromene-2,2′-indoline] with s-block ([Ca(MC)4](ClO4)2), d-block ([Zn(MC)2(MeCN)2](ClO4)2, [Ni(MC)2(MeCN)2](ClO4)2), as well as f-block ([La(NO3)3(MC)2]) metals. All complexes are structurally described by X-ray crystallography and systematically investigated in solution via Job’s method of continuous variations (Job plots), as well as online NMR spectroscopic kinetic experiments with in situ irradiation of the analyte solution inside the NMR spectrometer (LED-NMR). We can unambiguously identify the photoresponsive nature of the complexes in solution, which is a crucial step toward the application of these promising molecules in material science.

中文翻译:

使用在线LED-NMR研究Spiropyran金属配合物的光化学

作为研究最深入的光电开关之一,螺吡喃(SP)在科学界引起了极大的兴趣。在改变异构化为花青(MC)异构体的许多刺激因素中,例如温度,pH,溶剂极性,氧化还原电势或机械力中,MC形式作为金属络合配体位点的能力最近得到了提高。新的注意。我们在此合成了迄今未描述的带有s-block([Ca(MC)4 ]( ClO 42),d-嵌段([Zn(MC)2(MeCN)2 ](ClO 42,[Ni(MC)2(MeCN)2](ClO 42)和f嵌段([La(NO 33(MC)2 ])金属。所有配合物均通过X射线晶体学进行结构描述,并通过Job的连续变化方法(Job图)在溶液中进行系统研究,以及在线NMR光谱动力学实验,并NMR光谱仪(LED-NMR)中进行分析物溶液的原位照射)。我们可以明确地确定溶液中复合物的光响应性质,这是在材料科学中应用这些有前途的分子的关键一步。
更新日期:2019-10-27
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