Abstract
Because of the peculiar dynamic covalent reactivity of boronic acids to form tetraboronate derivatives, interest in using their aryl derivatives in materials science and supramolecular chemistry has risen. Nevertheless, their ability to form H-bonded complexes has been only marginally touched. Herein we report the first solution and solid-state binding studies of the first double-H-bonded DD·AA-type complexes of a series of aromatic boronic acids that adopt a syn-syn conformation with suitable complementary H-bonding acceptor partners. The first determination of the association constant (Ka) of ortho-substituted boronic acids in solution showed that Ka for 1:1 association is in the range between 300 and 6900 M-1. Crystallization of dimeric 1:1 and trimeric 1:2 and 2:1 complexes enabled an in-depth examination of these complexes in the solid state, proving the selection of the -B(OH)2 syn-syn conformer through a pair of frontal H-bonds with the relevant AA partner. Non-ortho-substituted boronic acids result in "flat" complexes. On the other hand, sterically demanding analogues bearing ortho substituents strive to retain their recognition properties by rotation of the ArB(OH)2 moiety, forming "T-shaped" complexes. Solid-state studies of a diboronic acid and a tetraazanaphthacene provided for the first time the formation of a supramolecular H-bonded polymeric ribbon. On the basis of the conformational dynamicity of the -B(OH)2 functional group, it is expected that these findings will also open new possibilities in metal-free catalysis or organic crystal engineering, where double-H-bonding donor boronic acids could act as suitable organocatalysts or templates for the development of functional materials with tailored organizational properties.
Original language | English |
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Pages (from-to) | 2710-2727 |
Number of pages | 18 |
Journal | Journal of the American Chemical Society |
Volume | 139 |
Issue number | 7 |
DOIs | |
Publication status | Published - 22 Feb 2017 |
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Dive into the research topics of 'Versatile Self-Adapting Boronic Acids for H-Bond Recognition: From Discrete to Polymeric Supramolecules'. Together they form a unique fingerprint.Equipment
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High Performance Computing Technology Platform
Champagne, B. (Manager)
Technological Platform High Performance ComputingFacility/equipment: Technological Platform
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Physical Chemistry and characterization(PC2)
Wouters, J. (Manager), Aprile, C. (Manager) & Fusaro, L. (Manager)
Technological Platform Physical Chemistry and characterizationFacility/equipment: Technological Platform
Datasets
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CCDC 1037401: Experimental Crystal Structure Determination
Bonifazi, D. (Contributor), Bruylants, G. (Contributor), De Leo, F. (Contributor), Georgiou, I. (Contributor), Kervyn, S. (Contributor), Rossignon, A. (Contributor) & Wouters, J. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2017
DOI: 10.5517/ccdc.csd.cc13thkz, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc13thkz&sid=DataCite
Dataset
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CCDC 1037393: Experimental Crystal Structure Determination
Bonifazi, D. (Contributor), Bruylants, G. (Contributor), De Leo, F. (Contributor), Georgiou, I. (Contributor), Kervyn, S. (Contributor), Rossignon, A. (Contributor) & Wouters, J. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2017
DOI: 10.5517/ccdc.csd.cc13th9q, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc13th9q&sid=DataCite
Dataset
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CCDC 1037387: Experimental Crystal Structure Determination
Bonifazi, D. (Contributor), Bruylants, G. (Contributor), De Leo, F. (Contributor), Georgiou, I. (Contributor), Kervyn, S. (Contributor), Rossignon, A. (Contributor) & Wouters, J. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2017
DOI: 10.5517/ccdc.csd.cc13th3j, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc13th3j&sid=DataCite
Dataset
Student theses
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Synthesis, optoelectronic properties and hydrogen-bond promoted organisation of heteroatom-doped polycyclic hydrocarbons
ROSSIGNON, A. (Author), VINCENT, S. (Supervisor), BONIFAZI, D. (Supervisor), APRILE, C. (Jury), VINCENT, S. (Jury), Gerbaux, P. (Jury) & Kivala, M. (Jury), 6 Jul 2020Student thesis: Doc types › Doctor of Sciences