Supramolecular Sandwiches: Halogen-Bonded Coformers Direct [2+2] Photoreactivity in Two-Component Cocrystals

Molecules

Dale C. Swenson¹  Leonard R. MacGillivray¹  Jay Quentin¹ 

[1] Department of Chemistry, University of Iowa, Iowa City, IA 52242, USA;

关键词: cocrystal;    crystal engineering;    halogen bonding;    photodimerization;    cyclobutane;    pedal motion;   

DOI  :  10.3390/molecules25040907

来源: DOAJ

【 摘 要 】

The halogen-bond (X-bond) donors 1,3- and 1,4-diiodotetrafluorobenzene (1,3-di-I-tFb and 1,4-di-I-tFb, respectively) form cocrystals with trans-1,2-bis(2-pyridyl)ethylene (2,2′-bpe) assembled by N···I X-bonds. In each cocrystal, 2(1,3-di-I-tFb)·2(2,2′-bpe) and (1,4-di-I-tFb)·(2,2′-bpe), the donor molecules support the C=C bonds of 2,2′-bpe to undergo an intermolecular [2+2] photodimerization. UV irradiation of each cocrystal resulted in stereospecific and quantitative conversion of 2,2′-bpe to rctt-tetrakis(2-pyridyl)cyclobutane (2,2′-tpcb). In each case, the reactivity occurs via face-to-face π-stacked columns wherein nearest-neighbor pairs of 2,2′-bpe molecules lie sandwiched between X-bond donor molecules. Nearest-neighbor C=C bonds are stacked criss-crossed in both cocrystals. The reactivity was ascribed to the olefins undergoing pedal-like motion in the solid state. The stereochemistry of 2,2′-tpcb is confirmed in cocrystals 2(1,3-di-I-tFb)·(2,2′-tpcb) and (1,4-di-I-tFb)·(2,2′-tpcb).

【 授权许可】

Unknown