Mixed cocrystal approach influences the yield for a [2+2] cycloaddition reaction within a halogen-bonded organic solid
The synthesis, crystal structure, and [2+2] cycloaddition photoreactivity of a halogen-bonded mixed cocrystal is reported. The cocrystal solid solution contains two isosteric donors, namely, 1,4-diiodoperchlorobenzene (C<sub>6</sub>I<sub>2</sub>Cl<sub>4</sub>) and iodoperchlorobenzene (C<sub>6</sub>ICl<sub>5</sub>), along with trans-1,2-bis(pyridin-4-yl)ethylene (BPE, C<sub>12</sub>H<sub>10</sub>N<sub>2</sub>) which behaves as a ditopic reactant molecule. The mixed cocrystal, namely, (C<sub>6</sub>I<sub>2</sub>Cl<sub>4</sub>)<sub>0.75</sub>·(C<sub>6</sub>ICl<sub>5</sub>)<sub>0.25</sub>·(BPE), is achieved since both halogen-bond donors are similar in shape and are interchangeable at equivalent crystallographic positions. The combination of I...N and Cl...N halogen bonds generates one-dimensional chains that engage in homogeneous π-stacks, thereby positioning a pair of reactant molecules in a suitable location to photoreact. Notably, the overall yield for the solid-state photoreaction is influenced by the initial molar ratio of the isosteric halogen-bond donors within the mixed cocrystal.
Authors
- Eric Bosch (ORCID: https://orcid.org/0000-0002-6465-1879)
- Ryan H. Groeneman (ORCID: https://orcid.org/0000-0002-4602-6287)
- Daniel K. Unruh (ORCID: https://orcid.org/0000-0002-2594-5786)
- Nicole M. Shapiro
- Mark D Govero
Institutions
- Missouri State University (US)
- University of Iowa (US)
- Webster University (US)
Publication Details
- Journal
- Acta Crystallographica Section C Structural Chemistry
- Published
- 2025-03-07
- DOI
- https://doi.org/10.1107/s2053229625001913
- Citations
- 1
- Primary Topic
- Crystallography and molecular interactions
- Type
- article
- Field-Weighted Citation Impact
- 1.75