Tuning the Structures of AsMo12 and AsW12 into Chiral Crystals by Introducing CH3CN and H2O

Abstract Abstract. The asymmetrical crystal [Na(15C5) 2 ][Na(15C5)] 2 (AsMo 12 O 40 )] · CH 3 CN ( 1 ) was synthesized. Interestingly, the huge α‐keggin ion AsMo 12 is distorted by introduction of CH 3 CN molecules and adopts a chiral assembly with space group P 4 . In contrast, the analogous compound AsW 12 co‐crystallizes with trace H 2 O molecules. The hydrogen atoms of H 2 O are positionally disordered with 50 % occupation to correlate with AsW 12 in space group P 4/ m . Solid and solution CD spectra indicate that the crystals of 1 are in R configuration. This leads to the conclusion that molybdenum has greater affinity toward organic CH 3 CN, whereas tungsten has greater affinity to inorganic H 2 O. Additionally, AsMo 12 shows greater deformability than AsW 12 . It is suggested that POMo shows a greater potential as chiral material than POW because of the flexibility of Mo. As a highlight, CH 3 CN can function as a general chiral inducer for the innovation of other chiral crystals, if fixed along one dimension.