Meso-tetrakis(3,4,5-trimethoxyphenyl)porphyrin derivatives: Synthesis, spectroscopic characterizations and adsorption of NO2
Meso-tetrakis(3,4,5-trimethoxyphenyl)porphyrin derivatives: Synthesis, spectroscopic characterizations and adsorption of NO2
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DOI：
10.1016/j.cej.2019.122005
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发表时间：
2019-11
影响因子：
15.1
通讯作者：
Raoudha Soury;M. Chaabene;M. Jabli;T. Saleh;R. Chaâbane;E. saint-Aman;F. Loiseau;Christain Philouze;A. Allouche;H. Nasri
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文献类型：
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作者：
Raoudha Soury;M. Chaabene;M. Jabli;T. Saleh;R. Chaâbane;E. saint-Aman;F. Loiseau;Christain Philouze;A. Allouche;H. Nasri
本工作的重点是新的材料的基础上添加的锌作为具体的金属中心，用于捕获NO2气体的DFT计算。本研究旨在合成游离碱型meso-四-（3，4，5-三甲氧基苯基）卟啉（H2 TTMP）（I）、meso-四-（3，4，5-三甲氧基苯基）卟啉锌（II）配合物[Zn（TTMP）]（II）和（4-氰基吡啶）meso-四-（3，4，5-三甲氧基苯基）卟啉锌（II）[Zn（TTMP）（4-CNpy）]（III）并对其光谱性质进行表征。（III）的X-射线分子结构表明，该五配位锌（II）配合物的晶格由平行于[0 0 1]方向的二维层状结构组成，并由C单键H <$Cg和Cg <$Cg π的分子间和分子内相互作用维持。值得注意的是，1.2埃的空隙和0.7埃的网格位于2D层之间。对三种卟啉衍生物进行了密度泛函理论计算，结果与红外光谱和紫外-可见光谱的实验数据一致。采用第一性原理密度泛函理论研究了有毒气体NO2分子在卟啉衍生物上的吸附行为。根据（Ⅰ）-（Ⅲ）分子的MEP和NO_2分子的MEP以及吸附能的计算，我们认为化合物（Ⅱ）具有最好的吸附作用。更重要的是，NO2在卟啉衍生物上化学吸附后，其光谱发生了明显的红移，尤其是II/NO2络合物的光谱，这为NO2的结合提供了一个很好的检测指标.因此，该光谱可用于检测NO2和卟啉衍生物的存在表明适当的性质，建立良好的NO2传感器。
This work focuses on new materials based on the addition of zinc as specifically metal centers for the capture of NO2gas with DFT calculations. This study aims at the synthesis and the spectroscopic characterizations of the free basemeso-tetrakis-,(3,4,5trimethoxyphenyl)porphyrin (H2TTMP) (I),mesotetrakis(3,4,5trimethoxyphenyl)porphyrinato)zinc(II) complex [Zn(TTMP)] (II) and the (4-cyanopyridine)meso-tetrakis - (3,4,5-trimethoxyphenyl)porphyrinato)zinc(II) [Zn(TTMP)(4-CNpy)] (III). X-ray molecular structure of (III) displays that the crystal lattice of the five-coordinated zinc(II) coordination compound, is made up of two dimensional layers parallel to the [0 0 1] direction sustained by Csingle bondH⋯Cg and Cg⋯Cg π inter and intra-molecular interactions. Notably, the presence of voids of 1.2 Å and a grid of 0.7 Å are located between the 2D layers. DFT calculations on the three porphyrin derivatives were carried out and results indicated an agreement with both IR and UV-vis experimental data. The adsorption behaviors of the toxic NO2gas molecules on the porphyrin derivatives were investigated using first-principles density functional theory. Based on the MEP of (I)–(III) molecules and the MEP of NO2and the calculation of the adsorption energies, we suggest that compound (II) has the best attraction. More importantly, after NO2chemi-sorption on porphyrin derivatives, a remarkable red-shift is observed in the optical spectra, especially for II/NO2complex, thus offering a good index to detect the binding of NO2. The optical spectra can therefore be used to detect the presence of NO2and porphyrin derivatives indicate appropriate properties to establish good NO2sensors.