Supramolecular chirogenesis in zinc porphyrins: Complexation with enantiopure thiourea derivatives, binding studies and chirality transfer mechanism

被引：6

作者：

Konrad, Nele ^{[1
]}

Meniailava, Darya ^{[1
,2
]}

Osadchuk, Irina ^{[1
,3
]}

Adamson, Jasper ^{[4
]}

Hasan, Mohammed ^{[5
]}

Clot, Eric ^{[3
]}

Aav, Riina ^{[1
]}

Borovkov, Victor ^{[1
,5
]}

Kananovich, Dzmitry G. ^{[1
]}

机构：

[1] Tallinn Univ Technol, Sch Sci, Dept Chem & Biotechnol, Akad Tee 15, EE-12618 Tallinn, Estonia

[2] Belarusian State Univ, Fac Phys, Nezavisimosti Av 4, Minsk 220030, BELARUS

[3] Univ Montpellier, ENSCM, CNRS, ICGM, Montpellier, France

[4] NICPB, Akad Tee 23, EE-12618 Tallinn, Estonia

[5] South Cent Univ Nationalities, Coll Chem & Mat Sci, 182 Minzu RD, Wuhan 430074, Hubei, Peoples R China

来源：

JOURNAL OF PORPHYRINS AND PHTHALOCYANINES | 2020年 / 24卷 / 5-7期

基金：

欧盟地平线“2020”;

关键词：

porphyrin; thiourea; chiral amine; chirality; circular dichroism; host-guest binding; TD-DFT; GAUSSIAN-BASIS SETS; CORRELATED MOLECULAR CALCULATIONS; DENSITY-FUNCTIONAL THEORY; AUXILIARY BASIS-SETS; CIRCULAR-DICHROISM; CORRELATION-ENERGY; ABSOLUTE-CONFIGURATION; EXCITATION-ENERGIES; ATOMS; APPROXIMATION;

D O I：

10.1142/S108842461950192X

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Complexation of three (1R,2R)-2-aminocyclohexyl arylthioureas (aryl = 3,5-bis(trifluoromethyl)phenyl; phenyl; 3,5-dimethylphenyl) as the guests to ZnTPP and ZnOFP hosts has been studied by means of UV-vis, CD spectroscopies and computational simulation. The complexation proceeds via coordination of the primary amino group to the zinc ion of the metalloporphyrin and induces a moderate circular dichroism signal in the Soret band of the porphyrins. The association constants increase with larger electron-withdrawing properties of the porphyrin host and larger electron-donating ability of the guest, indicating predominantly electrostatic (Lewis acid-base) character of the complexation. Computational study of the (1R,2R)-2-aminocyclohexyl-(3,5-bis(trifluoromethyl)phenyl)thiourea and ZnTPP complex revealed slight asymmetric distortion of the porphyrin plane caused by the chiral guest and additional it-ir interactions between the host and guest molecules. The calculated CD spectrum for the same system reproduces the experimentally observed one.

引用

页码：840 / 849

页数：10

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