Abstract
Self-assembled complexes utilizing the ditopic dative bond acceptor 1,3-diboronic acid with catechol and complementary U-shaped donors in the form of 1,8-dipyridylnaphthalenes (1,8-bis(4-pyridyl)naphthalene (DPN), 1,8-bis(4-ethylenylpyridyl)naphthalene (DEPN), and 1,8-bis(4-ethynylpyridyl)naphthalene (DAPN)) yielded discrete two-component structures. The assemblies exhibit “plug-in-socket” geometries. DFT calculations are consistent with the donor pyridyl and acceptor catecholate being electron poor and rich, respectively. The assemblies pack via π–π interactions and support the inclusion of a solvent (i.e., DPN, DAPN). The materials may form a basis for the design of complex B-based structures (e.g., supramolecular dyads).
Highlights
Self-assembly processes involving diboronic esters are increasingly prevalent in the design of complex supramolecular assemblies and architectures
The formation of each assembly was accomplished by forming chloroform solutions of the corresponding bipyridine, 1,3benzenediboronic acid, and catechol and subsequently placing either toluene (DPN and DEPN) or m-xylene (DAPN) in a loosely secured screw-capped vial
DPN, DEPN, and DAPN are attractive owing to the cofacial geometries of the 4-pyridyl groups (Scheme 2)
Summary
Self-assembly processes involving diboronic esters are increasingly prevalent in the design of complex supramolecular assemblies and architectures. Linear diboronic acids on crystallization with di- and tritopic pyridines as linkers, for example, have generated macrocycles and cages, respectively. Linear diboronic acids on crystallization with di- and tritopic pyridines as linkers, for example, have generated macrocycles and cages, respectively. The pyridine linkers to date have been based on divergent geometries (e.g., 4,4′-bipyridine), many of which draw inspiration from studies that aim to generate hydrogen-bond and metal-mediated frameworks and solids. While the assembly properties of boronic acids can be expected to enhance the structural chemistry of members of the 1,8-nap framework, derivatives of 1,8-nap have not been applied to self-assembly using B←N bonding. A combination of 1,8-bis(4-pyridyl)naphthalene (DPN), 1,8-bis(4-ethylenylpyridyl)naphthalene (DEPN), and 1,8-bis(4-ethynylpyridyl)naphthalene (DAPN) with 1,3-benzenediboronic acid catechol diester (1,3-BBEC) affords the discrete 1:1 assemblies DPN·1,3-BBEC, DEPN·1,3-BBEC, and DAPN·1,3-BBEC, respectively. The formation of each assembly was accomplished by forming chloroform solutions of the corresponding bipyridine, 1,3benzenediboronic acid, and catechol (ratio 1:1:2) and subsequently placing either toluene (DPN and DEPN) or m-xylene (DAPN) in a loosely secured screw-capped vial.
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