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. 2019 Aug 22;24(17):3059.
doi: 10.3390/molecules24173059.

A Divergent Alkyne Diol Directs [2 + 2] Photoreactivity in the Solid State: Cocrystal, Supramolecular Catalysis, and Sublimation Effects

Shalisa M Oburn  1 , Jay Quentin  1 , Leonard R MacGillivray  2
Affiliations

A Divergent Alkyne Diol Directs [2 + 2] Photoreactivity in the Solid State: Cocrystal, Supramolecular Catalysis, and Sublimation Effects

Shalisa M Oburn et al. Molecules. .

Abstract

2-butyne-1,4-diol (1,4-bd) is used as a divergent ditopic template that directs trans-1,2-bis (n-pyridyl) ethylene (n,n'-bpe, where n = n' = 3 or 4) to undergo an intermolecular [2 + 2] photodimerization in the solid state. The components of cocrystals [(1,4-bd)·(4,4'-bpe)]n and [(1,4-bd)·(3,3'-bpe)]n form 1D hydrogen-bonded polymers with n,n'-bpe assembled as infinite parallel stacks. The alkenes undergo [2 + 2] photocycloadditions to form rctt-tetrakis (n-pyridyl) cyclobutane (where n = 3 or 4). We demonstrate that the reactive solid involving 4,4'-bpe exhibits supramolecular catalysis.

Keywords: [2 + 2] photocycloaddition; divergent template; solid state; supramolecular catalysis.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Scheme 1
Scheme 1
Photoreactive cocrystals using (a) divergent 1,4-bd and (b) supramolecular catalysis.
Figure 1
Figure 1
X-ray structure [(1,4-bd)·(4,4′-bpe)]n: (a) ORTEP representation, (b) 1D hydrogen-bonded chains, (c) stacks of hydrogen-bonded chains, (d) stacked C = C bonds of 4,4′-bpe.
Figure 2
Figure 2
X-ray structure [(1,4-bd)·(3,3′-bpe)]n: (a) ORTEP representation; (b) 1D chains; (c) stacks of hydrogen-bonded chains; (d) stacked C = C bonds of 3,3′-bpe.
Figure 3
Figure 3
X-ray structure (rctt-3,3′-tpcb)·(H2O): (a) ORTEP representation; (b) 1D hydrogen-bonded chains (c) interdigitated 2D sheets with separate 2D sheets blue and green.
Figure 4
Figure 4
1H-NMR spectra (300 MHz, DMSO-d6) monitoring photoreactivity of [(1,4-bd)·(4,4′-bpe)]n at 50% catalyst loading of 1,4-bd (100 h UV exposure). UV-exposure time (t) indicated with stacked spectra.
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