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Structures and Reactivities of Cocrystals Involving Diboronic Acids and Bipyridines: In Situ Linker Reaction and 1D-to-2D Dimensionality Change via Crystal-to-Crystal Photodimerization
Journal article   Open access   Peer reviewed

Structures and Reactivities of Cocrystals Involving Diboronic Acids and Bipyridines: In Situ Linker Reaction and 1D-to-2D Dimensionality Change via Crystal-to-Crystal Photodimerization

Maria Guadalupe Vasquez-Rios, Gonzalo Campillo-Alvarado, Dale C. Swenson, Herbert Hopfl and Leonard R. MacGillivray
Chemistry : a European journal, Vol.28(25), pp.e202104604-n/a
05/02/2022
DOI: 10.1002/chem.202104604
PMCID: PMC9310599
PMID: 35274391
url
https://doi.org/10.1002/chem.202104604View
Published (Version of record)CC BY V4.0 Open Access

Abstract

Cocrystallizations of diboronic acids [1,3-benzenediboronic acid (1,3-bdba), 1,4-benzenediboronic acid (1,4-bdba) and 4,4'-biphenyldiboronic acid (4,4'-bphdba)] and bipyridines [1,2-bis(4-pyridyl)ethylene (bpe) and 1,2-bis(4-pyridyl)ethane (bpeta)] generated the hydrogen-bonded 1 : 2 cocrystals [(1,4-bdba)(bpe)(2)] (1), [(1,4-bdba)(bpeta)(2)] (2), [(1,3-bdba)(bpe)(2)(H2O)(2)] (3) and [(1,3-bdba)(bpeta)(2)(H2O)] (4), wherein 1,3-bdba involved hydrated assemblies. The linear extended 4,4'-bphdba exhibited the formation of 1 : 1 cocrystals [(4,4'-bphdba)(bpe)] (5) and [(4,4'-bphdba-me)(bpeta)] (6). For 6, a hemiester was generated by an in-situ linker transformation. Single-crystal X-ray diffraction revealed all structures to be sustained by B(O)-H center dot center dot center dot N, B(O)-H center dot center dot center dot O, O-w-H center dot center dot center dot O, O-w-H center dot center dot center dot N, C-H center dot center dot center dot O, C-H center dot center dot center dot N, pi center dot center dot center dot pi, and C-H center dot center dot center dot pi interactions. The cocrystals comprise 1D, 2D, and 3D hydrogen-bonded frameworks with components that display reactivities upon cocrystal formation and within the solids. In 1 and 3, the C=C bonds of the bpe molecules undergo a [2+2] photodimerization. UV radiation of each compound resulted in quantitative conversion of bpe into cyclobutane tpcb. The reactivity involving 1 occurred via 1D-to-2D single-crystal-to-single-crystal (SCSC) transformation. Our work supports the feasibility of the diboronic acids as formidable structural and reactivity building blocks for cocrystal construction.
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