• atomic force microscopy;
  • cation exchange;
  • hybrid organic–inorganic polyoxometalates;
  • self-assembly;
  • crystal engineering


Herein a library of hybrid Mn-Anderson polyoxometalates anions are presented: 1, [(MnMo6O18)((OCH2)3-C-(CH2)7CHCH2)2]3−; compound 2, [(MnMo6O18)((OCH2)3C-NHCH2C16H9)2]3−; compound 3, [(MnMo6O18)((OCH2)3C-(CH2)7CHCH2)1((OCH2)3C-NHCH2C16H9)1]3−; compound 4, [(MnMo6O18)((OCH2)3C-NHC(O)CH2CHCH2)2]3− and compounds 59, [(MnMo6O18)((OCH2)3C-NHC(O)(CH2)xCH3)2]), where x = 4, 10, 12, 14, and 18 respectively. The compounds resulting from the cation exchange of the anions 19 to give TBA (a) and DMDOA (b) salts, and additionally for compounds 1, 2 and 3, tetraphenylphosphonium (PPh4) (c) salts, are explored at the air/water interface using scanning force microscopy, showing a range of architectures including hexagonal structures, nanofibers and other supramolecular forms. Additionally the solid-state structures for compounds 1c, 2c, 4a, 6a, 9a, are presented for the first time and these investigations demonstrate the delicate interplay between the structure of the covalently derivatised hybrid organo-clusters as well as the ion-exchange cation types.