Versatile Self-Adapting Boronic Acids for H-Bond Recognition: From Discrete to Polymeric Supramolecules

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Résumé

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.

langue originaleAnglais
Pages (de - à)2710-2727
Nombre de pages18
journalJournal of the American Chemical Society
Volume139
Numéro de publication7
Les DOIs
étatPublié - 22 févr. 2017

Empreinte digitale

Boronic Acids
Acids
Bearings (structural)
Supramolecular chemistry
Crystal engineering
Association reactions
Derivatives
Functional materials
Materials science
Crystallization
Catalysis
Carboxylic acids
Functional groups
Conformations
Metals

Citer ceci

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title = "Versatile Self-Adapting Boronic Acids for H-Bond Recognition: From Discrete to Polymeric Supramolecules",
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.",
author = "Irene Georgiou and {Kervyn De Meerendre}, Simon and Alexandre Rossignon and {De Leo}, Federica and Johan Wouters and Gilles Bruylants and Davide Bonifazi",
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day = "22",
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T1 - Versatile Self-Adapting Boronic Acids for H-Bond Recognition

T2 - From Discrete to Polymeric Supramolecules

AU - Georgiou, Irene

AU - Kervyn De Meerendre, Simon

AU - Rossignon, Alexandre

AU - De Leo, Federica

AU - Wouters, Johan

AU - Bruylants, Gilles

AU - Bonifazi, Davide

PY - 2017/2/22

Y1 - 2017/2/22

N2 - 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.

AB - 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.

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U2 - 10.1021/jacs.6b11362

DO - 10.1021/jacs.6b11362

M3 - Article

AN - SCOPUS:85013420529

VL - 139

SP - 2710

EP - 2727

JO - J. Am. Chem. Soc.

JF - J. Am. Chem. Soc.

SN - 0002-7863

IS - 7

ER -