Redox-active, luminescent coordination nanosheet capsules containing magnetite

Abstract

Two-dimensional coordination nanosheets (CONASHs) are grown at the spherical liquid–liquid interface of a dichloromethane droplet in water to form zero-dimensional nano- and micro-capsules using a simple dropping method, a syringe-pump method, and an emulsion method. Reaction of 1,3,5-tris[4-(4′-2,2′:6′,2″-terpyridyl)phenyl]benzene (1) with Fe(BF4)2 affords electrochromic Fe(tpy)2 CONASH capsules and that of ligand 1 with ZnSO4 does photoluminescent Zn2(μ-O2SO2)2(tpy)2 CONASH capsules. Fe(tpy)2 CONASH capsules containing magnetite particles were produced by the syringe-pump method by adding magnetite to the aqueous phase, with the assembly and dispersion of the magnetite-containing CONASH capsules being easily controlled with a magnet. This indicates that physicochemically functional CONASH capsules are suitable for incorporating other functional materials to develop hybrid systems.

Multiterpyridyl Ligand/Cadmium(II) Coordination Polymer Nanosheets for Recoverable Luminescent Sensors

“…Based on the previous work, the ligand L was successfully synthesized by a Suzuki coupling reaction using 4′-(4-boronatophenyl)-2,2′:6′,2″-terpyridine and 1,3,5-tribromobenzene as reactants. − There are three functionalized terpyridyl groups in L, which can form stable coordination compounds with most transition cations due to the existence of d –π* feedback bonds between metal cations and the ligand. Through the interface-assisted synthetic method, − , a trichloromethane solution of L as the lower layer, Cd­(NO 3 ) 2 ·4H 2 O aqueous solution as the upper layer, finally, the cadmium coordination nanosheet (Cd-nanosheet) was obtained. The structure is shown in Figure (for clarity, the counteranions were omitted).…”

“…However, nitrobenzene has high stability and certain solubility in water, and the resulting water pollution can last for a long time. − In addition, an acute poisoning reaction (toxic methemoglobinemia) can occur when the human body inhales too much nitrobenzene, and in severe cases, it can lead to paralysis of the central nervous system and do great harm to human health. , Except for nitrobenzene, Cu 2+ ions have become one of the common pollution sources of soil and water due to copper mining and mechanical manufacturing. − At present, the rich electrochemical properties of coordination polymer nanosheets have been widely reported. They have attractive application prospects in solidified electrochromic devices, − microsupercapacitor devices, and flexible energy storage materials , due to their good redox activity. However, the luminescent properties of nanosheets are rarely studied.…”

“…33−35 At present, the rich electrochemical properties of coordination polymer nanosheets have been widely reported. They have attractive application prospects in solidified electrochromic devices, 36−38 microsupercapacitor devices, 39 and flexible energy storage materials 40,41 due to their good redox activity. However, the luminescent properties of nanosheets are rarely studied.…”

Chemically Laminated 2D Bis(terpyridine)metal Polymer Films: Formation Mechanism at the Liquid–Liquid Interface and Redox Rectification

“…We previously reported the synthesis and electrochromism of bis(terpyridine)metal CONASHs, Fe-tpy and Co-tpy, by using interfacial coordination reactions. [14,15] As bis(terpyridine)iron(II) and bis(terpyridine)cobalt(II) motifs have small dissociation reaction rate constants, [16] they are suitable for stepwise construction of heterolayer structures with insignificant transmetalation. [17,18] In the present work, we developed a sequential liquid-liquid interfacial coordination reaction method to realize structurally designable chemically laminated heterolayers (Figure 1, below).…”

“…We previously reported the synthesis and electrochromism of bis(terpyridine)metal CONASHs, Fe‐tpy and Co‐tpy, by using interfacial coordination reactions [14,15] . As bis(terpyridine)iron(II) and bis(terpyridine)cobalt(II) motifs have small dissociation reaction rate constants, [16] they are suitable for stepwise construction of heterolayer structures with insignificant transmetalation [17,18] .…”