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    Self-Assembly Properties of Amphiphilic Iron(III) Spin Crossover Complexes in Water and at the Air-Water Interface

    Year: 2018

    Journal: Magnetochemistry, Volume 4, DEC

    Authors: Martinho, Paulo N.; Kuhne, Irina A.; Gildea, Brendan; McKerr, George; O'Hagan, Barry; Keyes, Tia E.; Lemma, Tibebe; Gandolfi, Claudio; Albrecht, Martin; Morgan, Grace G.

    Organizations: Irish Research Council for Science, Engineering (IRCSET); Swiss National Science Foundation (SNSF) under the ERA-Chemistry programme; IRCSET Government of Ireland Research Scholarship; Fundacao para a Ciencia e a Tecnologia; University College Dublin; Irish Higher Education Authority; Irish Research Council (IRC) [GOIPD/2016/503]; Science Foundation Ireland [12/IP/1703]; COST Action [CM1305, CA15128, CA15107]

    Keywords: spin crossover; iron(III) amphiphile; micelle; Langmuir isotherm; Raman spectroscopy; lyophilization

    The assembly properties of three known spin crossover iron(III) complexes 1-3, at the air-water interface, are reported. All three complexes are amphiphiles, each bearing a pair of C-n alkyl chains on the polyamino Schiff base sal(2)trien ligand (n = 6, 12, or 18). Complex 1 is water-soluble but complexes 2 and 3 form Langmuir films, and attempts were made to transfer the film of the C-18 complex 3 to a glass surface. The nature of the assembly of more concentrated solutions of 3 in water was investigated by light scattering, cryo-SEM (scanning electron microscopy), and TEM (transmission electron microscopy), all of which indicated nanoparticle formation. Lyophilization of the assembly of complex 3 in water yielded a powder with a markedly different magnetic profile from the powder recovered from the initial synthesis, notably, the spin crossover was almost completely quenched, and the thermal behavior was predominantly low spin, suggesting that nanoparticle formation traps the system in one spin state.
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