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Abstract
Chemical bond lengths and angles are characteristic structural parameters of a molecule. Similarly, the frequencies of the vibrational modes and the NMR chemical shifts are unique "chemical fingerprints" specific to a compound. These are the basic parameters describing newly obtained compounds and enabling their identification. Intramolecular hydrogen bonding significantly influences the physicochemical properties of macrocyclic compounds with a porphyrin-like structure. This work presents the verification for correlations between geometric and spectroscopic parameters related to hydrogen bonds in this type of macrocyclic compounds. In particular, such relationships were investigated for a large group of porphyrin, porphycene, and dibenzotetraaza[14]annulene derivatives and a group of other macrocycles with similar structure. A very strong linear correlation was found only between the vibrational frequencies of the NH groups involved in a hydrogen bond and the length of this bond, which applied to all macrocyclic compounds of this type. Several other relationships were found between spectroscopic (IR, Raman, NMR) and geometric (X-ray) parameters, highlighting differences and similarities between different families of macrocycles. Apart from providing a better understanding of the nature of hydrogen bonds and their characteristics in porphyrin-like macrocyclic compounds, these relationships will facilitate the identification of new macrocycles and the extrapolation of their spectroscopic properties.
Supplementary materials
Title
Tables with the data taken for the analysis from the literature .
Description
Table S1. Experimental data points values of N…N distances, NH bond lengths, IR, Raman frequencies, and 1H chemical shifts of porphycenes.
Table S2. Experimental data points values of N…N distances, NH bond lengths, IR, Raman frequencies, and 1H chemical shifts of porphyrins.
Table S3. Experimental data points values of N…N distances, NH bond lengths, IR, and Raman frequencies, and 1H chemical shifts of dibenzotetraaza[14]annulenes.
Table S4. Experimental data points values of N…N distances, NH bond lengths, IR, and Raman frequencies, and 1H chemical shifts of different macrocycles with double intramolecular hydrogen bonds.
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