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[2]Rotaxanes Bearing a Tetralactam Macrocycle: The Role of a Trifurcated Hydrogen Bond in the Crystalline State
Author(s) -
Salbego Paulo R. S.,
Orlando Tainára,
Farias Fellipe F. S.,
Bonacorso Helio G.,
Martins Marcos A. P.
Publication year - 2019
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201900216
Subject(s) - chemistry , hydrogen bond , interaction energy , fragmentation (computing) , hydrogen , crystallography , molecule , computational chemistry , stereochemistry , organic chemistry , computer science , operating system
This study investigated the proper classification and quantification of intercomponent trifurcated hydrogen bonds, in the crystalline state, of rotaxanes bearing a tetralactam Leigh‐type macrocycle. Quantum mechanical calculations were carried out to obtain the interaction paths and their stabilization energies. In general, the use and necessity of fragmentation in types of interaction have been reported in the literature, although they are commonly performed only using a geometric approach. This results in N–H ··· O interactions that are indicated as the main interactions between components, neglecting other possible interactions. The use of energetic fragmentation was demonstrated here under an appropriate demarcation considering all interactions and showing the existence and role of the C–H ··· O interaction. The C–H ··· O interactions showed similar energy to N–H ··· O interactions with average values around –4.75 kcal mol –1 and –4.60 kcal mol –1 , respectively. This revealed that the three hydrogen bonds are part of a cooperative set of interactions with a similar contribution. The trifurcated hydrogen bonds presented high contribution in the total intercomponent stabilization energy of the rotaxanes, with an average value of 51 % in the studied series.