Square-like metallamacrocyclic palladium(II) complexes
[M8L4
]
8+
(1–7) were synthesized by reacting aromatic
dipyrazole ligands (H2L1–H2L3 with pyromellitic
arylimide-, 1,4,5,8-naphthalenetetracarboxylic arylimide-, and anthracene-based
aromatic groups, respectively) with dipalladium corners ([(bpy)2Pd2(NO3)2](NO3)2, [(dmbpy)2Pd2(NO3)2](NO3)2, or [(phen)2Pd2(NO3)2](NO3)2,
where bpy = 2,2′-bipyridine, dmbpy = 4,4′-dimethyl-2,2′-bipyridine,
and phen = 1,10-phenanthroline) in aqueous solutions via metal-directed
self-assembly. Metallamacrocycles 1–7 were fully
characterized by 1H and 13C nuclear magnetic
resonance spectroscopy and electrospray ionization mass spectrometry,
and the square structure of 7·8NO3
– was further confirmed via single crystal X-ray diffraction.
These square-like metallamacrocycles exhibit effective performance
for iodine adsorption.
By employing dipalladium corners [(bpy)(2)Pd(2)(NO(3))(2)](NO(3))(2) or [(phen)(2)Pd(2)(NO(3))(2)](NO(3))(2) (where bpy = 2,2'-bipyridine and phen = 1,10-phenanthroline) to bridge ferrocene-based dipyrazole ligand (L(1)) and m-phenylene-based dipyrazole ligands (L(2-3)) in aqueous solution, a series of positively-charged [M(4)L(2)](4+) metallomacrocycles were obtained. Their structures were characterized by (1)H NMR, electrospray ionization mass spectrometry (ESI-MS), elemental analysis, and single crystal X-ray diffraction analysis for 1·4NO(3) ({[(bpy)Pd](4)L(1)(2)}(NO(3))(4)) and 4·4NO(3) ({[(phen)Pd](4)L(2)(2)}(NO(3))(4)). In their single crystal structures, NO(3)(-) anions are located at the dipalladium corners by C-H...O hydrogen bonds. Importantly, the anion-sensing properties of ferrocene functionalized [Pd(4)Fe(2)] hetero-metallomacrocycle 1 were investigated in acetonitrile by SWV, CV and NMR analysis, showing promise for Br(-) sensing.
The aqueous self-assembly of the flexible ligand L bis(1H-benz[d]imidazole-1-yl)methane and cis-coordinated Pt precursors [(en)Pt , (tmeda)Pt , en=ethylenediamine, tmeda=N,N,N',N'-tetramethylethylenediamine)] led to the formation of the metallacalixarenes with full alternative conformations (e.g., two novel water-soluble metallacalixarenes [M L ] and [M L ] with D and D symmetry, respectively). Their molecular structures were determined by single crystal X-ray analyses in solid state. The two metallacalixarenes present different cavity sizes and the [M L ] cavity encapsulates one NO . NOESY NMR revealed that the conformational interconversion between 1,3-alternate conformer in methanol and cone conformer in DMSO was tuned via the synergistic effect between solvent and anion. Guest encapsulation is also discussed.
Superb control over the helical chirality of discrete (M3L2)n polyhedra (n = 2,4,8, M = CuI or AgI) created from the self-assembly of propeller-shaped ligands (L) equipped with chiral side...
Entangled (M 3 L 2 ) n polyhedral complexes represent a unique class of supramolecular architectures that are stabilized by relatively weak metal-acetylene interactions in cooperation with conventional metalpyridyl coordination. Counter-anion exchange of these complexes with a nitrate (NO 3 À ) ion triggered formal metal insertion between the metal centers, and a heteroleptic ternary coordination mode with acetylenic, pyridyl, and nitrate donors was generated on the metal centers. As a result, the main frameworks of the polyhedral complexes M 18 L 12 and M 12 L 8 were formally extended into a new series of concave polyhedra having the compositions M 21 L 12 and M 13 L 8 , respectively. This transformation also resulted in the local disconnection of the highly entangled trifurcate topology of the framework, providing clues toward the skeletal editing of extended and complex three-dimensional (3D) architectures.
Entangled (M3L2)n polyhedral complexes represent a unique class of supramolecular architectures that are stabilized by relatively weak metal–acetylene interactions in cooperation with conventional metal–pyridyl coordination. Counter‐anion exchange of these complexes with a nitrate (NO3−) ion triggered formal metal insertion between the metal centers, and a heteroleptic ternary coordination mode with acetylenic, pyridyl, and nitrate donors was generated on the metal centers. As a result, the main frameworks of the polyhedral complexes M18L12 and M12L8 were formally extended into a new series of concave polyhedra having the compositions M21L12 and M13L8, respectively. This transformation also resulted in the local disconnection of the highly entangled trifurcate topology of the framework, providing clues toward the skeletal editing of extended and complex three‐dimensional (3D) architectures.
Silver-acetylene interactions ……adopting aheteroleptic ternary coordination mode enabled synthesis of concave polyhedral cages upon anion-exchange-triggered interconversion of highly entangled polyhedra. In their Communication (e202303714), Yuya Domoto and co-workers describe skeletally edited 3D architectures having partially disconnected knot or link motifs at their polyhedral faces.
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