Synthesis and self-assembly of spin-labile and redox-active manganese(III) complexes
|Title:||Synthesis and self-assembly of spin-labile and redox-active manganese(III) complexes||Authors:||Gandolfi, Claudio
Martinho, Paulo N.
Morgan, Grace G.
|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|
Show full item record
This item is available under the Attribution-NonCommercial-NoDerivs 3.0 Ireland. No item may be reproduced for commercial purposes. For other possible restrictions on use please refer to the publisher's URL where this is made available, or to notes contained in the item itself. Other terms may apply.