Self-assembly of metallomacrocycles with dipyrazole ligands and anion sensing of [Pd₄Fe₂] macrocycle with ferrocene-based dipyrazole ligand

Abstract

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.

Construction of multiferrocenyl metallacycles and metallacages via coordination-driven self-assembly: from structure to functions

“…À salt of 54 that was obtained through anion exchange with 10-fold excess NH 4 PF 6 in a methanol solution) 22). 31 The structure of 59 was confirmed by X-ray crystallographic analysis, which revealed that the size of its inner square-shaped cavity was approximately 6 Â 11 Å (Fig. 22).…”

“…34). 41 Multinuclear NMR { 1 H and 31 P} spectroscopy, elemental analysis, and ESI-MS results provided strong evidence for the formation of multi-ferrocenyl cuboctahedron 94. For example, the 31 P { 1 H} NMR spectrum of 94 displayed a sharp singlet (B16.9 ppm) shifted upfield from that of the starting platinum acceptor 21 by B6.0 ppm.…”

“…These results firmly supported the complete conversion of hexagonal prism 103 into the postsynthetically modified species 105 maintaining the integrity of the prismatic core. For instance, similar to that of 100, the 31 Therefore, the post-self-assembly modification strategy provides an alternative approach to construct functionalized metallosupramolecules. In particular, it is very helpful for the construction of species that are not accessible via conventional coordination-driven self-assembly.…”

Recoverable Mechanoresponsive Luminescent Molecular Sponge Material: A Novel Aryl Gold(I) Isocyanide Compound

“…In recent decades, mechanoresponsive luminescent (MRL) materials have received a large amount of attention arising from their intrinsic nature, daedal structures, and characterization, as well as their potential applications. − Broadly, changes in crystal structure resulting from external mechanical stimulation led to luminescence changes. − For the aryl gold­(I) isocyanide compounds that exhibit MRL properties, the luminescence changes mainly refer to changes of halogen bond interactions and π···π interactions in the crystal structure. − Upon mechanical stimulation, a single-crystal-to-single-crystal phase transition accompanied by red-shifted or blue-shifted photoluminescence with incorporated weak or strong C–H···π interactions was reported by Ito . The same author also utilized chiral steric hindrance paired with aurophilic interactions to cause a chiral-crystal-to-achiral-crystal phase transition, which accompanied a change of emission properties .…”

Activation and Substitution of 1-Ferrocenylalkylamines with Allenones: Application to Three-Component Synthesis of 4-(1-Ferrocenylalkyl)pyrazoles

“…Thus, a one-pot, two-step, three-component synthesis was expected to provide unprecedented yet convenient access to 4-(1-ferrocenyl­alkyl)­pyrazoles, particularly chiral ones. It is noteworthy that some 4-(ferrocenyl­methyl)­pyrazole/metal complexes exhibit growth inhibitory activity against human cancer cell lines, promising anion-sensing properties, and interesting electrochemical behaviors . These simple 4-(ferrocenyl­methyl)­pyrazoles were reported to be prepared in two steps by substitution of ferrocenyl­methanol with 1,3-diketones followed by condensation with hydrazine.…”