Non‐Innocent π Linkers Affect Cooperativity in Hydrogen‐Bonded Macrocycles

Author:

Almacellas David1,van der Lubbe Stephanie C. C.2,Grosch Alice A.2ORCID,Tsagri Iris2,Vermeeren Pascal2ORCID,Poater Jordi13ORCID,Fonseca Guerra Célia2ORCID

Affiliation:

1. Departament de Química Inorgànica i Orgànica & IQTCUB Universitat de Barcelona Martí i Franquès 1–11 08028 Barcelona Spain

2. Department of Chemistry and Pharmaceutical Sciences, AIMMS Vrije Universiteit Amsterdam De Boelelaan 1108 1081 HZ Amsterdam The Netherlands

3. ICREA Passeig Lluís Companys 23 08010 Barcelona Spain

Abstract

AbstractRigid, linear π‐conjugated acetylene linkers connecting a hydrogen‐bond acceptor to a hydrogen‐bond donor are established building blocks for self‐assembled hydrogen‐bonded macrocycles. Kohn‐Sham molecular orbital and Voronoi deformation density analyses reveal that the acetylene linker plays an unprecedented, non‐innocent role in the cooperativity of these hydrogen‐bonded macrocycles. The acetylene linker can abstract electron density from the hydrogen‐bond acceptor and donor, due to the linkers’ low‐lying π‐LUMO. As a result, the hydrogen‐bond acceptor becomes less negatively charged, which both hampers the cooperativity, as well as the hydrogen bond strength, in the hydrogen‐bonded macrocycles. This effect becomes more pronounced when the size of the acetylene linker increases. The findings presented in this work can act as design principles for the development of novel supramolecular macrocycles based on hydrogen bonds.

Funder

Generalitat de Catalunya

Publisher

Wiley

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