title: Dual lanthanide role in the designed synthesis of hollow metal coordination (Prussian Blue analogue) nanocages with large internal cavity and mesoporous cage.
abstract: Prussian Blue (PB) analogue metal coordination nanocages comprised of mesoporous walls (ca. 3.5 nm pore width) encapsulating a cavity approaching ca. 100 nm in diameter (surfactant free) are presented as an advance in rational metal coordination polymer nanostructure design. The synthesis employs lanthanide ions (Gd(3+) or Er(3+)) which function initially as peripheral coordination crosslinkers of metallo-surfactant templated miniemulsion droplets, and, subsequently, as promoters in the removal of the organic component of those surfactants via metal-assisted ester hydrolysis. The success of this synthetic strategy relies entirely on the periphery coordination event occurring prior to the ester hydrolysis surfactant removal step. Crucially, this one-pot sequential synthesis was achieved using a newly developed metallo-surfactant designed to have a reduced ester hydrolysis rate. Syntheses of this innovative metallo-surfactant, intermediary PB analogue coordination polymer organo-nanoshells and the subsequent conversion to hollow metal coordination nanocages are fully characterised using a wide variety of techniques, including TEM, SEM, EFTEM, EDX, TGA, WAXD, NMR, N(2) adsorption, etc., and represent the first designed synthesis of hollow metal coordination nanocages containing a large nanoscale cavity (wall of hollow nanosphere is mesoporous; hence nanocage).
authors.affiliation: Department of Colour Science, School of Chemistry, University of Leeds, LS2 9JT, UK.
authors.forename: Ronan
authors.initials: R
authors.lastname: McHale
authors.forename: Yibo
authors.initials: Y
authors.lastname: Liu
authors.forename: Negar
authors.initials: N
authors.lastname: Ghasdian
authors.forename: Nicole S
authors.initials: NS
authors.lastname: Hondow
authors.forename: Sunjie
authors.initials: S
authors.lastname: Ye
authors.forename: Yun
authors.initials: Y
authors.lastname: Lu
authors.forename: Rik
authors.initials: R
authors.lastname: Brydson
authors.forename: Xiaosong
authors.initials: X
authors.lastname: Wang
mesh_terms: D005295:Ferrocyanides / Q000737:chemistry*; D006868:Hydrolysis; D028581:Lanthanoid Series Elements / Q000737:chemistry*; D049329:Nanostructures / Q000737:chemistry* / Q000648:ultrastructure; D010316:Particle Size; D011108:Polymers / Q000737:chemistry; D016062:Porosity; D013501:Surface-Active Agents / Q000737:chemistry
chemical_list: D005295:Ferrocyanides; D028581:Lanthanoid Series Elements; D011108:Polymers; D013501:Surface-Active Agents; C000170:ferric ferrocyanide