Developing Remote Metal Binding Sites in Heteropolymolybdates

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

“…The six protons attached to μ 3 -O atoms ( Figure 1A) of the Anderson-Evans POM in the B−type can be replaced with a wide variety of tris-ligands (RC(CH 2 OH) 3 , R = e.g. -NH 2 , -OH, -CH 2 OH, and further derivatization with imine and amide bonds either before or after attachment to the POM) [83,84]. The tris-ligands can be synthesized first and then be grafted onto the POM (pre-functionalization) or trisligands can further be modified by organic reactions after attachment onto the POM (postfunctionalization) [85].…”

Design of Hydrophobic Polyoxometalate Hybrid Assemblies Beyond Surfactant Encapsulation

“…We have been able to synthesize organic-inorganic hybrids by grafting Tris (Tris = tris(hydroxymethyl)amino methane, [(HOCH 2 ) 3 CNH 2 ]), onto the MnAnderson cluster via the alkoxo groups. The "free" reactive group -NH 2 on the other side of the Tris presents a route [24][25] to develop a new type of POM-containing materials. As a result, we have successfully grafted long (C-16 and C-18, see Scheme 1) alkyl-chains through covalent amide bonds to the Mn-Anderson cluster with the aim to develop robust POM-containing hybrid assemblies of surface-grafted clusters (SGCs).…”

Smart Self‐Assemblies Based on a Surfactant‐Encapsulated Photoresponsive Polyoxometalate Complex

“…By grafting the azobenzene (Azo) group [12] covalently onto the Mn-Anderson-type cluster through a tris(hydroxymethyl)aminomethane connector ( Figure S1 in the Supporting Information), [10] we prepared a novel photoresponsive surfactant-encapsulated organically grafted polyoxometalate (SEOP), as shown in Scheme 1 a.…”

“…Therefore, the fabrication of novel aggregate structures and smart POM assemblies will be of topical interest. [9] To carry out photocontrolled supramolecular assembly in POM-based systems, we combined both organic grafting [10] of photoisomerizable groups and electrostatic encapsulation [7c] onto one POM unit to realize the present proposition. The prepared complex building block can form self-assemblies in solution, and smart morphological changes between fibrous and spherical aggregates are successfully achieved for the first time through tuning the multiple supramolecular interactions by photoirradiation.…”