2009
DOI: 10.1039/b902262g
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Structural features directing the specificity and functionality of metallo-supramolecular grid-type architectures

Abstract: New ditopic bis-hydrazone type ligands possessing various functional units have been designed to self-assemble into axially and laterally decorated [2 x 2] grids with octahedrally coordinating metal ions. Solution and solid state investigations have provided evidence for the strong influence of the nature of the attached groups on the structure and function of these metallo-supramolecular entities. Various techniques were applied in order to explore the magnetic, optical and structural properties of these func… Show more

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Cited by 40 publications
(18 citation statements)
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“…Again this is a relatively young area of investigation, with few reported Fe 4 L 4 grids in the literature, and even fewer examples that exhibit SCO. In fact only 21 ligands (Chart 11) have been reported to produce SCO-active Fe 4 grids, 39,[127][128][129][130][131][132][133][134][135][136][137] the first of which was reported in 2000 -this was also the first example of an SCO-active tetranuclear complex, 127 and held the record for the largest nuclearity discrete SCO-active complex until 2009 (see the 'nanoball' later). Interestingly, 16 of the ligands employed to date feature pyrimidine-bridging moieties L50-L65 À (only 6 of the resulting grids have been structurally characterised, one in two different spin states, Table 8), whilst the other 5 ligands, L66 À to L70 (all of the resulting grids have been structurally characterised, Table 9), present a wide range of different bridging moieties (Chart 11).…”
Section: Tetrametallic Anion-bridged Fe 4 Squaresmentioning
confidence: 99%
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“…Again this is a relatively young area of investigation, with few reported Fe 4 L 4 grids in the literature, and even fewer examples that exhibit SCO. In fact only 21 ligands (Chart 11) have been reported to produce SCO-active Fe 4 grids, 39,[127][128][129][130][131][132][133][134][135][136][137] the first of which was reported in 2000 -this was also the first example of an SCO-active tetranuclear complex, 127 and held the record for the largest nuclearity discrete SCO-active complex until 2009 (see the 'nanoball' later). Interestingly, 16 of the ligands employed to date feature pyrimidine-bridging moieties L50-L65 À (only 6 of the resulting grids have been structurally characterised, one in two different spin states, Table 8), whilst the other 5 ligands, L66 À to L70 (all of the resulting grids have been structurally characterised, Table 9), present a wide range of different bridging moieties (Chart 11).…”
Section: Tetrametallic Anion-bridged Fe 4 Squaresmentioning
confidence: 99%
“…In fact they have produced more than half of the known SCO-active Fe(II) grids in the literature. The other ligands used by them are also based on the pyrimidine bridging unit, but these ligands contain functionalised bis-hydrazone side arms and either pyridine 130,131 [(L57) À and L58-L62, Chart 11] or imidazole/thiazole 132 (L63 and L64, Chart 11) rings, and various substitutions thereof, to complete the terdentate binding pockets. In each case where SCO was observed the transition was very gradual and incomplete across a wide thermal range.…”
Section: Tetrametallic Anion-bridged Fe 4 Squaresmentioning
confidence: 99%
“…Some examples are present in the literature of cobalt complexes with acylhydrazonic ligands, with formation of mononuclear and polynuclear metal complexes [39][40][41]. During the synthesis in the presence of NEt 3 , Co(II) is oxidized to Co(III) and the ionic complex As also recently reported in the literature, acylhydrazones could be suitable ligands for the synthesis of multinuclear copper complexes [8,42].…”
Section: Chemistrymentioning
confidence: 90%
“…This band, which is common in hydrazone systems, corresponds to π-π* transitions present in the imine bond (C=N) of the hydrazone moiety and the ones found in the pyridine and pyrimidine rings (Wang, et al, 2010;Yu, et al, 2016). In contrast with the free ligand, the Zn 2+ grid complex exhibited two bands in the visible region corresponding to the abovementioned π-π* transitions; the bathochromic shift present in the complex can be explained by the extended conjugation in the grid structure (Stefankiewicz, et al, 2009).…”
Section: Synthesis Of the Organic Ligand 2-(4-butylphenyl)-46bis((e)mentioning
confidence: 98%
“…Bis(hydrazones) have allowed the synthesis of different grid-like structures with a wide range of metal cations (Hardy, 2013;Stefankiewicz, et al, 2009). However, the solubility of these ligands tends to be low, affecting the grid formation and the yields of the final product.…”
Section: Introductionmentioning
confidence: 99%