Exploring the Interplay Between Ligand Derivatisation and Cation Type in the Assembly of Hybrid Polyoxometalate Mn‐Andersons

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.

The Anderson–Evans polyoxometalate: From inorganic building blocks via hybrid organic–inorganic structures to tomorrows “Bio-POM”

“…The research group of Hasenknopf has since their first report on tris-functionalization successfully grafted 2-pyridinecarbaldehyde to Mn III Mo 6 and Fe III Mo 6 systems [83]. Other successfully attached ligands by the research group includes terpyridine ligands [269] and pendant pyridyl groups [276] resulting in the anions illustrated in Figure 11A Rosnes et al [182] have symmetrically attached alkyl chains of different lengths onto the Mn III Mo 6 core ranging from C 4 to C 20 via tris-like moieties (C 17 shown in Figure 11D). The chain length affects the surface architecture giving rise to different fibrous assemblies with different heights.…”

“…The reaction media can also be exchanged with DMF making it possible to use ligands that are not soluble in acetonitrile and the desired cations may be directly introduced, even small inorganic cations [178]. Since then symmetric post-functionalization (Figure 7, A3) has been achieved with a variety of organic ligands including ligands containing aromatic units [181] and alkyl-chains [182] of different lengths (see section 5.2).…”

Charge transport through redox active [H7P8W48O184]33− polyoxometalates self-assembled onto gold surfaces and gold nanodots

“…40-41 42 43-45 In those cases no special order in the POM arrangement was sought. As POMs are negatively charged species their immobilization onto electrodes has also commonly relied on their entrapment into positively charged polymers [46][47][48] or on the dip-coating exchange of their counter cations: by positively charged electrolyte through the Layer-by-Layer method to build photo-or electro-chromic materials, [49][50] photo-electrodes, 51 interfacial layers for solar cells [52][53][54] or multilayer films for electrocatalysis; [55][56][57] by amphiphilic cations to form Langmuir Blodgett films; [58][59][60][61][62] by positively charged groups directly decorating the electrode, 63 for application in water splitting, [64][65][66][67][68] molecular cluster batteries 69 or molecular electronics. 17,[70][71] Finally but to a lesser extent, covalent grafting of POMs onto electrodes, directly or in two steps, has been investigated by some of us and others.…”

Photoluminescence Properties of Two Closely Related Isostructural Series Based on Anderson-Evans Cluster Coordinated With Lanthanides [Ln(H2O)7{X(OH)6Mo6O18}]•yH2O, X = Al, Cr

“…Anderson-Evans cluster, as it has been known since, is made of six edge-shared distorted {MoO 6 } octahedra and the central cavity thus formed is occupied by slightly flattened, X(OH) 6 , heteroatom octahedron. The cluster assumes a near D 3d symmetry with dimensions ~8.6 × 8.6 × 2.7 Å and has been isolated with fifteen different heteroatoms till now [X: Al (Lee et al, 1991; Manikumari et al, 2002; Shivaiah et al, 2002; Martin et al, 2004; Shivaiah and Das, 2005; Liu et al, 2006; Dhara et al, 2007; Cao et al, 2008; Zhou et al, 2009), Cr (Perloff, 1970; An et al, 2006; Yu et al, 2006; Lee, 2007; Zhou and Yang, 2007; Shi D. et al, 2008; Shi D. M. et al, 2008; Zhang et al, 2008, 2014; Singh et al, 2010b, 2014; Li et al, 2011; Singh and Ramanan, 2011; Kumar et al, 2014a; Joo et al, 2015), Mn (He et al, 2012; Oms et al, 2012; Rosnes et al, 2012, 2013; Yan et al, 2012; Zhang et al, 2012, 2015a,b; Hutin et al, 2013; Ai et al, 2014; Yvon et al, 2014), Fe (Wu et al, 2001), Co (Nolan et al, 1996; Panneerselvam et al, 1996; Lee and Joo, 2000a; Lee et al, 2001; Martin et al, 2004), Ni (Lee et al, 2002; Liu et al, 2007; Liu F.-X. et al, 2008), Cu (Ito et al, 1989), Zn (Allen et al, 1997), Ga (Mensinger et al, 2008; Himeno et al, 2009), Te (Evans, 1948; Kondo et al, 1980; Robl and Frost, 1993a,b; Lorenzo-Luis et al, 1999; Drewes et al, 2004a,b; Charushnikova et al, 2005; Drewes and Krebs, 2005; Gao et al, 2007; Liu Y. et al, 2008; Yan et al, 2008), Rh (Ozawa et al, 1991), Pd (Ozawa et al, 1991), Sb (Ogawa et al, 1988; Yan et al, 2014), I (Kondo et al, 1980; Rosu and Weakley, 2000; An et al, 2...…”