Metalloporphyrin Metal–Organic Frameworks: Eminent Synthetic Strategies and Recent Practical Exploitations

Abstract

The emergence of metal–organic frameworks (MOFs) in recent years has stimulated the interest of scientists working in this area as one of the most applicable archetypes of three-dimensional structures that can be used as promising materials in several applications including but not limited to (photo-)catalysis, sensing, separation, adsorption, biological and electrochemical efficiencies and so on. Not only do MOFs have their own specific versatile structures, tunable cavities, and remarkably high surface areas, but they also present many alternative procedures to overcome emerging obstacles. Since the discovery of such highly effective materials, they have been employed for multiple uses; additionally, the efforts towards the synthesis of MOFs with specific properties based on planned (template) synthesis have led to the construction of several promising types of MOFs possessing large biological or bioinspired ligands. Specifically, metalloporphyrin-based MOFs have been created where the porphyrin moieties are either incorporated as struts within the framework to form porphyrinic MOFs or encapsulated inside the cavities to construct porphyrin@MOFs which can combine the peerless properties of porphyrins and porous MOFs simultaneously. In this context, the main aim of this review was to highlight their structure, characteristics, and some of their prominent present-day applications.

Integrating the multiple functionalities in metalloporphyrin porous organic polymers enabling strong polysulfide anchoring and rapid electrochemical kinetics in Li–S batteries

“…Among the coordinated metals, Mg and Co atoms are two of the most important naturally occurring metalloporphyrins found in chlorophylls and vitamin B12, respectively. 26 The formed imidazolium-containing connectors endow the POP with LiPS trapping, electrolyte affinity, and ionic dissociation functions originating from their high intrinsic polarity, polarizability, and ion conduction. On the one hand, the ion-conductive linkers integrate the Por(M) active sites within the porous structure for easy accessibility of liquid electrolytes and effectively decoupled charge transport in electrolytes.…”

Enhanced Solid-State Fluorescence of Flavin Derivatives by Incorporation in the Metal-Organic Frameworks MIL-53(Al) and MOF-5

“…The incorporation of luminescent dye molecules into metal-organic frameworks (MOFs) as a dye@MOF composite tries to exploit the photophysical properties of single molecules in a well-defined solid-state environment for applications such as white-light emission, upconversion, non-linear optics, biological fluorescent imaging, chemical sensing, optical thermometry and others [ 18 , 19 , 20 , 21 , 22 , 23 ]. The structure and pore environment of MOF compounds can be designed by the selection of organic linkers and the metal cluster secondary building units (SBUs) [ 24 , 25 , 26 , 27 , 28 , 29 , 30 , 31 ]. Through incorporation into MOFs, the dye molecules could be protected from dynamic quenching, e.g., by O 2 or solvent interactions.…”

Formation of Gold Nanoclusters from Goldcarbonyl Chloride inside the Metal-Organic Framework HKUST-1

“…Metal-organic frameworks (MOFs) [ 1 , 2 , 3 , 4 ] are potentially porous and mostly crystalline three-dimensional solids, which attract considerable attention in a wide range of envisioned applications [ 5 ], e.g., in catalysis [ 6 ], hydrogen storage [ 7 ], separations [ 8 ], as sensors [ 9 , 10 , 11 ], for nanocluster formation [ 12 , 13 ], or precursors for electrocatalysts [ 12 , 14 , 15 ]. Open metal sites (OMSs), also named coordinatively unsaturated metal sites (CUSs), at the metal center possess a crucial role in some applications [ 16 , 17 , 18 ].…”