Exploring the interplay between ligand derivatisation and cation type in the assembly of hybrid polyoxometalate Mn-Andersons

Herein a library of hybrid Mn-Anderson polyoxometalates anions are presented: 1, [(MnMo6O18)((OCH2) 3-C-(CH2)7CHCH2)2] 3-; compound 2, [(MnMo6O18)((OCH 2)3C-NHCH2C16H9) 2]3-; compound 3, [(MnMo6O18) ((OCH2)3C-(CH2)7CHCH 2)1((OCH2)3C-NHCH2C 16H9)1]3-; compound 4, [(MnMo 6O18)((OCH2)3C-NHC(O)CH 2CHCH2)2]3- and compounds 5-9, [(MnMo6O18)((OCH2)3C-NHC(O)(CH 2)xCH3)2]), where x = 4, 10, 12, 14, and 18 respectively. The compounds resulting from the cation exchange of the anions 1-9 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 derivatise...