The First One‐Pot Synthesis of Metal–Organic Frameworks Functionalised with Two Transition‐Metal Complexes

The synthesis of a metal–organic framework (UiO‐67) functionalised simultaneously with two different transition metal complexes (Ir and Pd or Rh) through a one‐pot procedure is reported for the first time. This has been achieved by an iterative modification of the synthesis parameters combined with characterisation of the resulting materials using different techniques, including X‐ray absorption spectroscopy (XAS). The method also allows the first synthesis of UiO‐67 with a very wide range of loadings (from 4 to 43 mol %) of an iridium complex ([IrCp*(bpydc)(Cl)Cl]^2?; bpydc=2,2′‐bipyridine‐5,5′‐dicarboxylate, Cp*=pentamethylcyclopentadienyl) through a pre‐functionalisation methodology.     

Interactive Thermal Effects on Metal–Organic Framework Polymer Composite Membranes

Polymeric membranes are important tools for intensifying separation processes in chemical industries, concerning strategic tasks such as CO₂ sequestration, H₂ production, and water supply and disposal. Mixed‐matrix and supported membranes have been widely developed; recently many of them have been based on metal–organic frameworks (MOFs). However, most of the impacts MOFs have within the polymer matrix have yet to be determined. The effects related to thermal behavior arising from the combination of MOF ZIF‐8 and polysulfone have now been quantified. The catalyzed oxidation of the polymer is strongly affected by the MOF crystal size and distribution inside the membrane. A 16 wt % 140 nm‐sized ZIF‐8 loading causes a 40 % decrease in the observed activation energy of the polysulfone oxidation that takes place at a temperature (545 °C) 80 °C lower than in the raw polymer (625 °C).     

Synchronizing Substrate Activation Rates in Multicomponent Reactions with Metal–Organic Framework Catalysts

A study on the influence of the cation coordination number, number of Lewis acid centers, concurrent existence of Lewis base sites, and structure topology on the catalytic activity of six new indium MOFs, has been carried out for multicomponent reactions (MCRs). The new indium polymeric frameworks, namely [In₈(OH)₆(popha)₆(H₂O)₄]?3 H₂O ( InPF‐16 ), [In(popha)(2,2′‐bipy)]?3 H₂O ( InPF‐17 ), [In₃(OH)₃(popha)₂(4,4′‐bipy)]?4 H₂O ( InPF‐18 ), [In₂(popha)₂(4,4′‐bipy)₂]?3 H₂O ( InPF‐19 ), [In(OH)(Hpopha)]?0.5 (1,7‐phen) ( InPF‐20 ), and [In(popha)(1,10‐phen)]?4 H₂O ( InPF‐21 ) (InPF=indium polymeric framework, H₃popha=5‐(4‐carboxy‐2‐nitrophenoxy)isophthalic acid, phen=phenanthroline, bipy=bipyridine), have been hydrothermally obtained by using both conventional heating (CH) and microwave (MW) procedures. These indium frameworks show efficient Lewis acid behavior for the solvent‐free cyanosilylation of carbonyl compounds, the one pot Passerini 3‐component (P‐3CR) and the Ugi 4‐component (U‐4CR) reactions. In addition, InPF‐17 was found to be a highly reactive, recyclable, and environmentally benign catalyst, which allows the efficient synthesis of α‐aminoacyl amides. The relationship between the Lewis base/acid active site and the catalytic performance is explained by the 2D seven‐coordinated indium framework of the catalyst InPF‐17 . This study is an attempt to highlight the main structural and synthetic factors that have to be taken into account when planning a new, effective MOF‐based heterogeneous catalyst for multicomponent reactions.     

Modulation of the Physicochemical Properties of Donor–Spiro–Acceptor Derivatives through Donor Unit Planarisation: Phenylacridine versus Indoloacridine—New Hosts for Green and Blue Phosphorescent Organic Light‐Emitting Diodes (PhOLEDs)

This work reports a detailed structure–property relationship study of a series of efficient host materials based on the donor–spiro–acceptor (D‐spiro‐A) design for green and sky‐blue phosphorescent organic light‐emitting diodes (PhOLEDs). The electronic and physical effects of the indoloacridine (IA) fragment connected through a spiro bridge to different acceptor units, namely, fluorene, dioxothioxanthene or diazafluorene moiety, have been investigated in depth. The resulting host materials have been easily synthesised through short, efficient, low‐cost, and highly adaptable synthetic routes by using common intermediates. The dyes possess a very high triplet energy (E_T) and tuneable HOMO/LUMO levels, depending on the strength of the donor/acceptor combination. The peculiar electrochemical and optical properties of the IA moiety have been investigated though a fine comparison with their phenylacridine counterparts to study the influence of planarisation. Finally, these molecules have been incorporated as hosts in green and sky‐blue PhOLEDs. For the derivative SIA‐TXO₂ as a host, external quantum efficiencies as high as 23 and 14 % have been obtained for green and sky‐blue PhOLEDs, respectively.