Developing Luminescent Ratiometric Thermometers Based on a Covalent Organic Framework (COF)

Covalent Organic Frameworks (COFs), an emerging class of crystalline porous materials, are proposed as a new type of support for grafting lanthanide ions (Ln³⁺) and employing these hybrid materials as ratiometric luminescent thermometers. A TpBpy‐COF—prepared from 1,3,5‐triformylphloroglucinol (Tp) and 2,2′‐bipyridine‐5,5′‐diamine (Bpy) grafted with Eu/Tb and Dy acetylacetone (acac) complexes can be successfully used as a luminescent thermometer in the 10–360 K (Eu) and 280–440 K (Tb) ranges with good sensing properties (thermal sensitivity up to 1.403 % K^?1, temperature uncertainty δT<1 K above 110 K). For the Eu/Tb systems, we observe an unusual and rarely reported behavior, that is, no thermal quenching of the Tb³⁺ emission, a result of the absence of ion‐to‐ligand/host energy back‐transfer. The LnCOF materials proposed here could be a new class of materials employed for temperature‐sensing applications following up on the well‐known luminescent metal–organic framework thermometers.     

Inside Back Cover: Integrated Soft Porosity and Electrical Properties of Conductive-on-Insulating Metal-Organic Framework Nanocrystals (Angew. Chem. Int. Ed. 35/2023)

A one-stone, two-bird method to integrate the soft porosity and electrical properties of distinct metal–organic frameworks (MOFs) into a single material involves the design of conductive-on-insulating MOF (cMOF-on-iMOF) heterostructures that allow for direct electrical control. Herein, we report the synthesis of cMOF-on-iMOF heterostructures using a seeded layer-by-layer method, in which the sorptive iMOF core is combined with chemiresistive cMOF shells. The resulting cMOF-on-iMOF heterostructures exhibit enhanced selective sorption of CO₂ compared to the pristine iMOF (298 K, 1 bar, S from 15.4 of ZIF-7 to 43.2–152.8). This enhancement is attributed to the porous interface formed by the hybridization of both frameworks at the molecular level. Furthermore, owing to the flexible structure of the iMOF core, the cMOF-on-iMOF heterostructures with semiconductive soft porous interfaces demonstrated high flexibility in sensing and electrical “shape memory” toward acetone and CO₂. This behavior was observed through the guest-induced structural changes of the iMOF core, as revealed by the operando synchrotron grazing incidence wide-angle X-ray scattering measurements.     

Back Cover: Metal-Organic Framework Supported Copper Photoredox Catalysts for Iminyl Radical-Mediated Reactions (Angew. Chem. Int. Ed. 21/2023)

Visible-light copper photocatalysis has recently emerged as a viable technology for building sustainable synthetic processes. To broaden the applications of phosphine-ligated copper(I) complexes, we describe herein an effective metal-organic framework (MOF)-supported copper(I) photocatalyst for multiple iminyl radical-mediated reactions. Due to site isolation, the heterogenized copper photosensitizer has a significantly higher catalytic activity than its homogeneous counterpart. Using a hydroxamic acid linker to immobilize copper species on MOF supports affords the heterogeneous catalysts with high recyclability. The post-synthetic modification sequence on MOF surfaces allows for the preparation of previously unavailable monomeric copper species. Our findings highlight the potential of using MOF-based heterogeneous catalytic systems to address fundamental challenges in the development of synthetic methodologies and mechanistic investigations of transition-metal photoredox catalysis.     

Inside Back Cover: Retina-Inspired Organic Photonic Synapses for Selective Detection of SWIR Light (Angew. Chem. Int. Ed. 6/2023)

Photonic synapses with the dual function of optical signal detection and information processing can simulate human visual system. However, photonic synapses with selective detection of short-wavelength infrared (SWIR) light have never been reported, which can not only broaden the human vision region but also integrate neuromorphic computation and infrared optical communication. Here, organic photonic synapses based on a new donor-acceptor copolymer P1 are fabricated, which exhibit excellent synaptic characteristics with selective detection for SWIR and extremely low energy consumption (2.85 fJ). The working mechanism is rooted in energy level barriers and unbalanced charge transportation. Moreover, these photonic synapses demonstrate excellent performance in multi-signal logic editing, letter imaging and memory with noise reduction function. This contribution provides ideas of constructing selective-response synapses for artificial visual system and neuromorphic computing.