文献类型：期刊文献

英文题名：Computational study of aromaticity, 1H NMR spectra and intermolecular interactions of twisted thia-norhexaphyrin and its multiply annulated polypyrrolic derivatives

作者：Baryshnikov, Gleb V.[1,2];Valiev, Rashid R.[3,4];Li, Qizhao[5];Li, Chengjie[5];Xie, Yongshu[5];Agren, Hans[1,6]

机构：[1]KTH Royal Inst Technol, Sch Engn Sci Chem Biotechnol & Hlth, Div Theoret Chem & Biol, S-10691 Stockholm, Sweden;[2]Bohdan Khmelnytsky Natl Univ, Dept Chem & Nanomat Sci, UA-18031 Cherkassy, Ukraine;[3]Natl Res Tomsk Polytech Univ, Res Sch Chem & Appl Biomed Sci, Lenin Ave 30, Tomsk 634050, Russia;[4]Univ Helsinki, Dept Chem, FIN-00014 Helsinki, Finland;[5]East China Univ Sci & Technol, Sch Chem & Mol Engn, Key Lab Adv Mat & Joint Int Res Lab Precis Chem &, Shanghai 200237, Peoples R China;[6]Henan Univ, Coll Chem & Chem Engn, Kaifeng 475004, Henan, Peoples R China

年份：2019

卷号：21

期号：45

起止页码：25334

外文期刊名：PHYSICAL CHEMISTRY CHEMICAL PHYSICS

收录：;EI(收录号：20201708553100);WOS:【SCI-EXPANDED(收录号:WOS:000506841300045)】；

基金：This work was supported by the Ministry of Education and Science of Ukraine (project no. 0117U003908), and by the Olle Engkvist Byggmastare foundation (contract no. 189-0223). The calculations were performed with computational resources provided by the High Performance Computing Center North (HPC2N) in Umea, Sweden, through the project ''Multiphysics Modeling of Molecular Materials'' SNIC 2018-2-38. The GIMIC calculations were carried out using the SKIF supercomputer at the Tomsk State University. The work at ECUST was financially supported by Shanghai Municipal Science and Technology Major Project (Grant No. 2018SHZDZX03) and the international Cooperation Program of Shanghai Science and Technology Committee (17520750100), NSFC (21772041, 21702062, 21811530005), and Program of Introducing Talents of Discipline to Universities (B160170). R. R. Valiev thanks the Academy of Finland (1325369) and is personally thankful to the Tomsk Polytechnic University Competitiveness Enhancement Program (VIU-RSCABS-142/2019).

语种：英文

外文关键词：Aromatic compounds - Hydrogen bonds - Computation theory - Aromatization - Nuclear magnetic resonance spectroscopy

摘要：The recently synthesized twisted thia-norhexaphyrin and its multiply annulated polypyrrolic derivatives have been studied computationally. Gauge-including magnetically induced current calculations predict a global nonaromatic character of the initial thia-norhexaphyrin due to the highly-twisted conformation of the macrocycle. Upon the oxidation of the thia-norhexaphyrin four multiply annulated polypyrrolic aromatic macrocycles are formed for which the global aromatic character is confirmed in agreement with experimentally measured H-1 NMR spectra. The calculation of the proton chemical shifts for the studied compounds by direct comparison with the tetramethylsilane standard leads to a significant mean absolute error. At the same time a linear regression procedure for the two selected groups of protons (CH and NH protons) provides much better values of calculated chemical shifts and tight correlation with experiment. The separate consideration of NH protons is motivated by the numerous intermolecular hydrogen bonds in which the protons are involved, which induce considerable upfield shifts, leading to a significant underestimation of the corresponding chemical shifts. Such a selected correlation can be used for accurate estimation of proton chemical shifts of the related porphyrinoids. Bader's theory of Atoms in Molecules has been applied for the studied twisted thia-norhexaphyrin and its multiply annulated polypyrrolic derivatives to characterize intramolecular H-bonds and other non-covalent interactions.