Exploring the Interplay Between Ligand Derivatisation and Cation Type in the Assembly of Hybrid Polyoxometalate Mn‐Andersons. Issue 13 (7th February 2013)

• Record Type: Journal Article
• Authors: Rosnes, Mali H.; Musumeci, Chiara; Yvon, Carine; Macdonell, Andrew; Pradeep, Chullikkattil P.; Sartorio, Camillo; Long, De‐Liang; Pignataro, Bruno; Cronin, Leroy
• Is Part Of: Small. Volume 9:Issue 13(2013:Jul.)
• Page Start: 2316
• Page End: 2324
• Publication Date: 2013-02-07
• Subjects: atomic force microscopy -- cation exchange -- hybrid organic–inorganic polyoxometalates -- self‐assembly -- crystal engineering; Nanotechnology -- Periodicals; Nanoparticles -- Periodicals; Microtechnology -- Periodicals; 620.5
• DOI: 10.1002/smll.201202510
• Languages: English
• ISSNs: 1613-6810

Abstract

Abstract: Herein a library of hybrid Mn‐Anderson polyoxometalates anions are presented: 1, [(MnMo6 O18 )((OCH2 )3 ‐C‐(CH2 )7 CHCH2 )2 ] 3− ; compound 2, [(MnMo6 O18 )((OCH2 )3 C‐NHCH2 C16 H9 )2 ] 3− ; compound 3, [(MnMo6 O18 )((OCH2 )3 C‐(CH2 )7 CHCH2 )1 ((OCH2 )3 C‐NHCH2 C16 H9 )1 ] 3− ; compound 4, [(MnMo6 O18 )((OCH2 )3 C‐NHC(O)CH2 CHCH2 )2 ] 3− and compounds 5 –9, [(MnMo6 O18 )((OCH2 )3 C‐NHC(O)(CH2 )x CH3 )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 derivatised hybrid organo‐clusters as well as the ion‐exchange cation types. Abstract : A thorough investigation of nine hybrid Mn‐Anderson polyoxometalate self‐assembly architectures, both in crystal structures and on surfaces, is carried out. The clusters are obtained with various cations, which influence their self‐assembly at interfaces, resulting in structures such as hexagonal nanocrystals, nanofibers, and other supramolecular forms. Using hybrid POMs as building blocks serves as a toolbox for future self‐assembly investigations, where a series of variables can be tuned to provide well‐defined complex structures.