A Chinese Pane-Like 2D Metal-Organic Framework Showing Magnetic Relaxation and Luminescence Dual-Functions

Abstract

The discovery of graphene kicked off the curtain of atom-type two-dimensional (2D) materials. Layered metal-organic frameworks (MOFs) as parallel molecule-based 2D materials are more designable and more diverse, and magnetism may be induced by their metal ion nodes. However, the multifunctional 2D plane-like MOFs are very difficult to obtain. Here we describe a Chinese pane-like 2D MOF constructed from the Ln3+ cation and the nanoscale luminescent tritopic ligand tris(4′-carboxybiphenyl)-amine, responding to the slow magnetic relaxation and luminescence properties, respectively. Notably, the Dy-Dy distances separated by the tritopic ligand are up to 2 nm. Such a 2D molecular material is expected to have potential applications in optoelectronics and multimodal sensing.

Fast and Robust Synthesis of Metalated PCN-222 and Their Catalytic Performance in Cycloaddition Reactions with CO2

“…These materials all gave similar diffraction patterns (see Figure S6) and were formed in yields of (71.6 ± 1.3)% on a scale of 100 mg/batch. Thus, this procedure affords significantly increased overall yields in a short synthesis time frame …”

“…The use of a modulator as well as the molar ratio modulator/Zr 4+ were crucial; importantly, the amount of PCN-222 obtained decreased when increased amounts of 2FBA were used, irrespective of the other reaction parameters (see Table S3). We hypothesize that the presence of 2FBA decreases the solubility of Zr preclusters in the reaction medium; 49 this would allow less modulator to be used than in syntheses where benzoic acid was used. In general, neither reaction temperature nor reaction time had any dramatic effect on the final yield (see Table S3).…”

“…Thus, this procedure affords significantly increased overall yields in a short synthesis time frame. 49 It must be mentioned that this procedure cannot be extended to the synthesis of TCPP(Fe), probably as a consequence of the ability of Fe 2+ cations to interact with the −COO − groups of the linker. Cross-linked two-dimensional polymeric Fe-TCPP structures have been reported elsewhere.…”

Incorporation of expanded organic cations in dysprosium(III) borohydrides for achieving luminescent molecular nanomagnets

“…The majority of synthetic strategies applied in the construction of emissive SMMs take advantage of expanded organic ligands which are responsible both for constraining the coordination geometry of 4f metal ion towards strong single-ion anisotropy as well as sensitizing its luminescence through ligand-to-metal energy transfer 18 , 35 . Alternatively, luminescent molecular nanomagnets can be obtained by the incorporation of lanthanide ions into coordination frameworks, including metal–organic frameworks 36 , 37 , based on organic linkers or d-block metalloligands 38 – 40 . The up-to-date reported routes toward emissive SMMs explore rather sophisticated lanthanide(III) moieties exploring complicated organic ligands or a multi-component approach demanding the second metal complex 18 , 39 , 40 .…”

Fine Tuning the Energy Barrier of Molecular Nanomagnets via Lattice Solvent Molecules

“…Recently, we found a chain-like azido-bridged manganese(III) coordination polymer showing both solvatomagnetic effect and spin-glass behaviour 10 . In studies of single molecule magnets (SMMs) 11 , we also hope to explore SMM systems with solvatomagnetic effects. However, it is a great challenging task because most SMMs reported are concentrated on zero-dimensional (0 D) cluster or mononuclear systems.…”