Certain types of porphyrins can be used as achiral agent for determination of enantiomeric excess (ee) of chiral molecules. Particular organic chiral molecule (guest) and porphyrin (host) form host-guest complex while inducing nonequiv- alency of particular proton resonances in symmetrical host. It causes splitting of NMR signals linearly dependent on ee of guest. In this work we investigated com- plexation of di-brombenzylated oxoporphyrin with chiral camphorsulfonic acid. NMR titration revealed that they form complex with 1:1 stoichiometry with as- sociation constant K ≈ 5 × 104 l/mol. We confirmed linear dependence of split- ting of host β-protons on ee of guest. Low temperature measurements revealed two conformations of host-guest complex with population around 0.7:0.3 (at −60 ◦ C). DFT quantum mechanical computations at BLYP/3-21G* level revealed also two conformations with population 0.79:0.21. NMR shifts were computed on this geometries with method GIAO/PBE1PBE/6-31G(2df,2pd) and compared to experimental values. 1
Identifer | oai:union.ndltd.org:nusl.cz/oai:invenio.nusl.cz:336614 |
Date | January 2014 |
Creators | Březina, Václav |
Contributors | Hanyková, Lenka, Šoltésová, Mária |
Source Sets | Czech ETDs |
Language | English |
Detected Language | English |
Type | info:eu-repo/semantics/masterThesis |
Rights | info:eu-repo/semantics/restrictedAccess |
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