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Crystal structure and photoreactivity of a halogen‐bonded cocrystal based upon 1,2‐diiodoperchlorobenzene and 1,2‐bis(pyridin‐4‐yl)ethylene
Author(s) -
Bosch Eric,
Battle Jessica D.,
Groeneman Ryan H.
Publication year - 2020
Publication title -
acta crystallographica section c
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.304
H-Index - 17
ISSN - 2053-2296
DOI - 10.1107/s2053229620006233
Subject(s) - cocrystal , halogen , ethylene , cyclobutane , crystallography , halogen bond , molecule , chemistry , yield (engineering) , crystal (programming language) , solvent , photochemistry , cycloaddition , materials science , ring (chemistry) , organic chemistry , hydrogen bond , catalysis , alkyl , computer science , metallurgy , programming language
The formation of a photoreactive cocrystal based upon 1,2‐diiodoperchlorobenzene ( 1,2‐C 6 I 2 Cl 4 ) and trans ‐1,2‐bis(pyridin‐4‐yl)ethylene ( BPE ) has been achieved. The resulting cocrystal, 2( 1,2‐C 6 I 2 Cl 4 )·( BPE ) or C 6 Cl 4 I 2 ·0.5C 12 H 10 N 2 , comprises planar sheets of the components held together by the combination of I…N halogen bonds and halogen–halogen contacts. Notably, the 1,2‐C 6 I 2 Cl 4 molecules π‐stack in a homogeneous and face‐to‐face orientation that results in an infinite column of the halogen‐bond donor. As a consequence of this stacking arrangement and I…N halogen bonds, molecules of BPE also stack in this type of pattern. In particular, neighbouring ethylene groups in BPE are found to be parallel and within the accepted distance for a photoreaction. Upon exposure to ultraviolet light, the cocrystal undergoes a solid‐state [2 + 2] cycloaddition reaction that produces rctt ‐tetrakis(pyridin‐4‐yl)cyclobutane ( TPCB ) with an overall yield of 89%. A solvent‐free approach utilizing dry vortex grinding of the components also resulted in a photoreactive material with a similar yield.