Synthesis and self-assembly of spin-labile and redox-active manganese(III) complexes

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Title: Synthesis and self-assembly of spin-labile and redox-active manganese(III) complexes
Authors: Gandolfi, Claudio
Cotting, Tatiana
Martinho, Paulo N.
Morgan, Grace G.
Albrecht, Martin
et al.
Permanent link: http://hdl.handle.net/10197/6819
Date: 7-Mar-2011
Abstract: New amphiphilic and spin-labile Mn-III complexes based on dianionic N4O2-hexadentate sal(2)trien or sal(2)bapen ligands, which contain OC6H13, OC12H25, or OC18H37 alkoxy substituents at different positions of the salicylidene unit were prepared (H(2)sal(2)trien = N, N"'-bis(salicylidene)-1,4,7,10-tetraazadecane, H(2)sal(2)bapen = N, N"'-bis(salicylidene)-1,5,8,12-tetraazadodecane). According to electrochemical measurements, these complexes undergo two (quasi) reversible redox processes. Temperature-dependent magnetic measurements revealed a high-spin configuration for all sal(2)trien complexes (S = 2) and gradual spin crossover for sal(2)bapen complexes from high to low spin (S = 1). The chain length strongly influences the spin crossover, as C-18-functionalization stabilizes the low spin state at much higher temperatures than shorter alkyl chains. Moreover, long alkyl chains allow for spontaneous self-assembly of the molecules, which was investigated in single crystals and in Langmuir-films at the air-water interface. Long alkyl chains (C-12 or C-18) as well as a mutual syn-orientation of these molecular recognition sites were required for the Langmuir monolayers to be stable.
Type of material: Journal Article
Publisher: Royal Society of Chemistry
Copyright (published version): 2011 the Royal Society of Chemistry
Keywords: Langmuir-blodgett-films;Phase-transition;Room-temperature;Magnetic-properties;Iron(II) complexes;Crystal-structures;Coordination nanoparticles;Physical-properties;Molecular-structure;Crossover behavior
DOI: 10.1039/c0dt01222j
Language: en
Status of Item: Peer reviewed
Appears in Collections:Chemistry Research Collection

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