Journal article
Halogen versus Hydrogen Bonding in Binary Cocrystals: Novel Conformation a Coformer with [2+2] Photoreactivity of Criss‐Crossed C=C Bonds
Chemphyschem, Vol.21(2), pp.154-163
01/16/2020
DOI: 10.1002/cphc.201900961
PMID: 31600417
Abstract
A series of cocrystals involving the hydrogen‐ and halogen‐bond donor coformers catechol (cat) and 1,2‐diiodotetrafluorobenzene (1,2‐di‐I‐tFb), respectively, is reported. Each coformer forms a cocrystal with each of the three symmetric bipyridines trans‐1,2‐bis(n‐pyridyl)ethylene (n,n′‐bpe, where: n=n′=2, 3, 4). Four novel cocrystals (cat) ⋅ (3,3′‐bpe), 2(1,2‐di‐I‐tFb) ⋅ (2,2′‐bpe), 2(1,2‐di‐I‐tFb) ⋅ (3,3′‐bpe), and (1,2‐di‐I‐tFb) ⋅ (4,4′‐bpe) comprise components that assemble by either O−H⋅⋅⋅N hydrogen bonds (cat) or N⋅⋅⋅I halogen bonds (1,2‐di‐I‐tFb). In (cat) ⋅ (3,3′‐bpe), cat acts as a template to support an intermolecular [2+2] photocycloaddition of 3,3′‐bpe. The reactivity occurs via a one‐dimensional (1D) hydrogen‐bonded tape with stacked and criss‐crossed olefins that react stereoselectively and quantitatively to form rctt‐tetrakis(3‐pyridyl)cyclobutane (3,3′‐tpcb). The reactivity of the criss‐crossed olefins is facilitated by a hitherto not reported cis‐gauche conformation adopted by cat. The stereochemistry of 3,3′‐tpcb is confirmed in the cocrystal 2(cat) ⋅ (3,3′‐tpcb).
A structural comparison of halogen – versus hydrogen‐bonded cocrystals affords entry to a novel photoactive solid with criss‐crossed alkene C=C bonds.
Details
- Title: Subtitle
- Halogen versus Hydrogen Bonding in Binary Cocrystals: Novel Conformation a Coformer with [2+2] Photoreactivity of Criss‐Crossed C=C Bonds
- Creators
- Jay Quentin - University of IowaLeonard R MacGillivray - University of Iowa
- Resource Type
- Journal article
- Publication Details
- Chemphyschem, Vol.21(2), pp.154-163
- DOI
- 10.1002/cphc.201900961
- PMID
- 31600417
- ISSN
- 1439-4235
- eISSN
- 1439-7641
- Number of pages
- 10
- Grant note
- National Science Foundation (LRM DMR-1708673)
- Language
- English
- Date published
- 01/16/2020
- Academic Unit
- Pharmaceutical Sciences and Experimental Therapeutics; Chemistry
- Record Identifier
- 9984216565002771
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