Hexanuclear manganese metallamacrocycles with tripled hydrophobic tails

Novel 24-membered octanuclear manganese(III) metallacrown

“…The local environment of each metal centre of high-spin d 4 Mn(III) ion has the same JahnTeller elongated octahedral geometry as in other manganese metallamacrocycles [6]. The JahnTeller distortion results in elongation of the axial manganese-oxygen/nitrogen bond lengths by ~ 0.3 Å relative to the other Mn-O/N bond lengths.…”

“…A variety of metallamacrocycles and cages were found to form interesting hostguest systems with different metal ions of varying coordination and symmetry [5]. Metal ions such as Ga, Co, Fe and Mn that can easily form stable octahedral coordination, are found to yield hexanuclear metallamacrocycles with trianionic pentadentate ligands [6]. However manganese and iron have received special attention because of their ease of formation of metallamacrocycles and interesting magnetic properties [7].…”

A mixed-type of azametallacrown containing [Mn6(pnhz)6(DMF)4(H2O)2] and [Mn6(pnhz)6(DMF)2(H2O)4] constructed by a flexible pentadentate ligand

“…The self-assembly of the high-nuclear azaMCs with rigid N-terminal ligands has been intensively and, to some extent, successfully investigated [14][15][16][17][18][19][20][21][22][23][24], while of less interest is the exploration of the highly flexible N-terminal groups in such system, which may adjust various geometric modes to satisfy the requirements of assembly process and lead to interestingly structural topologies. Moreover, only few examples have been reported concerning the flexible N-terminal ligands, where diversely geometric configurations of the ligands are involved in one kind of 18-MC-6 [25,26]. To the best of our knowledge, no examples in which differently structural azaMCs appear simultaneously in one stable crystalline solid were found, not to mention those with the diversely N-substituted configuration.…”

“…S4b). Remarkably, compared with rare examples where diverse N-terminal groups are unsymmetrically located in one ring [25,26], the N-propionyl ends of I and II in complex 1 exhibit two disparate modes of symmetrical conformation, which may be one of the most complicated metallamacrocycle structure, never found in coordination chemistry of cyclic arrangements. The average 0.6032 Å deviation of the Mn ion from the least square plane in II is slightly larger than that of 0.5903 Å in It is to be noted that the complex 1 further assembles the extraordinary 3-D supramolecular MOF using two different aza18-MC-6 as SBUs via intermolecular C-HÁ Á Áp, p-p and C-HÁ Á ÁO non-covalent interactions.…”

A novel 18-membered metallacrown containing a double-azathiacrown

“…The dihydrazide derivative template ligands (Fig. 1a) were used to synthesize the second type of metallacrowns, the rings of the metallacrowns were expanded from 15-MC-5 to 18-MC-6 [11][12][13][14][15], 24-MC-8 [16,17], 30-MC-10 [18,19], 36-MC-12 [20,21], even to 60-MC-20 [22].…”