Papers

Peer-reviewed
Mar, 2016

Construction of Chiral Polar Crystals from Achiral Molecules by Stacking Control of Hydrogen-Bonded Layers Using Type II Halogen Bonds

CRYSTAL GROWTH & DESIGN
  • Toshiyuki Sasaki
  • ,
  • Yoko Ida
  • ,
  • Ichiro Hisaki
  • ,
  • Seiji Tsuzuki
  • ,
  • Norimitsu Tohnai
  • ,
  • Gerard Coquerel
  • ,
  • Hisako Sato
  • ,
  • Mikiji Miyata

Volume
16
Number
3
First page
1626
Last page
1635
Language
English
Publishing type
Research paper (scientific journal)
DOI
10.1021/acs.cgd.5b01724
Publisher
AMER CHEMICAL SOC

Crystals belonging to PI and P2(1) space groups are fascinating research targets because of their potential applications in various fields by taking advantage of their chirality and polarity. However, molecules intrinsically prefer symmetric, achiral nonpolar space groups due to canceling out of dipole moments and close packing in crystalline states. Therefore, it remains difficult to selectively obtain the P1 and P2(1) crystals, especially from achiral molecules. Here we achieve construction of the chiral P1 and P2(1) crystals from achiral molecules based on stacking control of chiral two-dimensional hydrogen-bonded layers by halogen bonds (XBs). Precise investigations and theoretical calculations of their crystal structures revealed that space group selectivity among the chiral P1, P2(1), and achiral space groups is the result of a subtle balance between the stronger interaction: charge-assisted hydrogen bonds and the weaker interactions: van der Waals interaction of alkyl chains and the bonding involving halogens, which have anisotropic nature and robustness-tunability. It is also noteworthy that type II XBs were observed in chiral crystals, while type I halogen center dot center dot center dot halogen contacts were formed in achiral crystals, indicating the importance of type II XBs for chiral crystallization.

Link information
DOI
https://doi.org/10.1021/acs.cgd.5b01724
Web of Science
https://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=JSTA_CEL&SrcApp=J_Gate_JST&DestLinkType=FullRecord&KeyUT=WOS:000371453900060&DestApp=WOS_CPL
URL
http://www.scopus.com/inward/record.url?partnerID=HzOxMe3b&scp=84959548883&origin=inward
ID information
  • DOI : 10.1021/acs.cgd.5b01724
  • ISSN : 1528-7483
  • eISSN : 1528-7505
  • SCOPUS ID : 84959548883
  • Web of Science ID : WOS:000371453900060

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