An official website of the United States government
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⋅⋅⋅N, B(O)−H⋅⋅⋅O, Ow−H⋅⋅⋅O, Ow−H⋅⋅⋅N, C−H⋅⋅⋅O, C−H⋅⋅⋅N, π⋅⋅⋅π, and C−H⋅⋅⋅π 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.
more »
« less
Light‐Induced Disruption of 1D Wire‐Like Arrays of Monoatomic Ag(I) Ions: Single‐Crystal Reaction with Crystal Softening
Abstract The exploitation of noncovalent bonding in the solid state is attractive to generate one‐dimensional (1D) wire‐like assemblies of metals and uncover dynamic and physical properties of such intriguing structures. Herein, we describe a metal‐organic crystal based on Ag(I) ions that assemble to be organized into 1D wire‐like assemblies maintained by argentophilic interactions. UV‐light irradiation of the crystal composed of the 1D structures results in a single‐crystal‐to‐single‐crystal (SCSC) photodimerization that transforms the 1D periodic metal arrays to isolated metal dimers. The structural reconfiguration creates small voids in the crystal and the resulting solids exhibit a substantial increase in softness up to 60%.
more »
« less
- Award ID(s):
- 2221086
- PAR ID:
- 10587088
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Angewandte Chemie International Edition
- Volume:
- 64
- Issue:
- 26
- ISSN:
- 1433-7851
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract The family of molecular level low‐dimensional organic metal halide hybrids has expanded significantly over the last few years. Here a new type of 1D metal halide structure is reported, in which metal halide octahedra form a corrugated double‐chain structure via nonplanar edge‐sharing. This material with a chemical formula of C5H16N2Pb2Br6exhibits a broadband yellow emission under ultraviolet light excitation with a photoluminescence quantum efficiency of around 10%. The light‐yellow emission is considered to be attributed to self‐trapping excitons. Theoretical calculations show that the unique alignment of the octahedra leads to small band dispersion and large exciton binding energy. Together with previously reported 1D metal halide wires and tubes, this new bulk assembly of 1D metal halides suggests the potential to develop a library of bulk assemblies of metal halides with controlled structures and compositions.more » « less
-
The organic metal halide hybrids welcome a new member with a one-dimensional (1D) tubular structure. Herein we report the synthesis and characterization of a single crystalline bulk assembly of organic metal halide nanotubes, (C 6 H 13 N 4 ) 3 Pb 2 Br 7 . In a metal halide nanotube, six face-sharing metal halide dimers (Pb 2 Br 9 5− ) connect at the corners to form rings that extend in one dimension, of which the inside and outside surfaces are coated with protonated hexamethylenetetramine (HMTA) cations (C 6 H 13 N 4 + ). This unique 1D tubular structure possesses highly localized electronic states with strong quantum confinement, resulting in the formation of self-trapped excitons that give strongly Stokes shifted broadband yellowish-white emission with a photoluminescence quantum efficiency (PLQE) of ∼7%. Having realized single crystalline bulk assemblies of two-dimensional (2D) wells, 1D wires, and now 1D tubes using organic metal halide hybrids, our work significantly advances the research on bulk assemblies of quantum-confined materials.more » « less
-
Abstract Naturally occurring polymeric structures often consist of 1D polymer chains intricately folded and entwined through non‐covalent bonds, adopting precise topologies crucial for their functionality. The exploration of crystalline 1D polymers through dynamic covalent chemistry (DCvC) and supramolecular interactions represents a novel approach for developing crystalline polymers. This study shows that sub‐angstrom differences in the counter‐ion size can lead to various helical covalent polymer (HCP) topologies, including a novel metal‐coordination HCP (m‐HCP) motif. Single‐crystal X‐ray diffraction (SCXRD) analysis of HCP−Na revealed that double helical pairs are formed by sodium ions coordinating to spiroborate linkages to form rectangular pores. The double helices are interpenetrated by the unreacted diols coordinating sodium ions. The reticulation of the m‐HCP structure was demonstrated by the successful synthesis of HCP−K. Finally, ion‐exchange studies were conducted to show the interconversion between HCP structures. This research illustrates how seemingly simple modifications, such as changes in counter‐ion size, can significantly influence the polymer topology and determine which supramolecular interactions dominate the crystal lattice.more » « less
