Direct, One-Pot Syntheses of MOFs Decorated with Low-Valent Metal-Phosphine Complexes

Abstract

We demonstrate a simple and generalizable method for the one pot, in situ formation of bimetallic metal–organic framework (MOF) materials decorated with crystallographically defined, low-valent metal sites. Solvothermal reactions between poly­(carboxylated) aryl­(phosphine) ligands and mixtures of higher- and lower-valent metal precursors achieves concomitant P–M complexation and MOF formation via metal–carboxylate network bonding. This method is demonstrated in the preparation of two new phosphine coordination materials, PCM-107 and PCM-74, which feature Ar3P–AuX (X = Cl, Br) and chelated –Cu2I2– units as the MOF building blocks, respectively. PCM-107 is an active catalyst for alkyne hydroaddition, while PCM-74 shows promise for the crystallization of MOFs bearing kinetically favored isomers.

Isolating reactive metal-based species in Metal–Organic Frameworks – viable strategies and opportunities

“…Specically, a one pot, in situ formation of bimetallic MOF was demonstrated where low-valent phosphine metal complexes could be crystallographically characterised. 115 The concomitant complexation of the phosphorus centre with a low valent metal and MOF formation via a metal-carboxylate network with a high valent node occurs without interference, to afford two new phosphine coordination materials, PCM-107 and PCM-74. These materials feature Ar 3 P-AuX (X ¼ Cl, Br) and chelated Cu 2 I 2 units (P-N coordinated) in their nal structures.…”

Water Adsorption Properties of Fe(pz)[Pt(CN)4] and the Capture of CO2 and CO

“…6 Indeed, in order to gain even more control over their structure and properties, MOFs can be modified "a la carte" via postsynthetic transformations, as was masterfully described by Humphrey and co-workers. 7 In addition, MOFs have been used successfully in various fields of science and technology; for example, as chemical sensors, 8 proton-conducting materials, 9 magnetic materials, 10 and heterogeneous catalysts for organic synthesis, 11 as well as molecular warehouses for gases of interest in chemical industry, 12 such as oxygen, 13 hydrogen, 14 and methane. 15 However, the use of novel MOFs to capture gases involved in air pollution and global warming is one of their most important applications and an issue still worthy of investigation.…”

“…In addition, MOFs have a designable or tunable microporosity, depending essentially on the structure of their organic ligands (main building units) . Indeed, in order to gain even more control over their structure and properties, MOFs can be modified “a la carte” via postsynthetic transformations, as was masterfully described by Humphrey and co-workers . In addition, MOFs have been used successfully in various fields of science and technology; for example, as chemical sensors, proton-conducting materials, magnetic materials, and heterogeneous catalysts for organic synthesis, as well as molecular warehouses for gases of interest in chemical industry, such as oxygen, hydrogen, and methane .…”

Boronate Covalent and Hybrid Organic Frameworks Featuring PIII and P=O Lewis Base Sites

“…The presence of lone electron pair at the P III centers provides a possibility for pre ‐ or post ‐synthetic functionalization through alkylation, arylation or chalcogenation . Such materials are also considered as solid‐state ligands (SSLs) for coordination of transition metals . Regarding the latter ability, the most common strategy involves the formation of robust coordination polymers with metals (Ca, Zr, Sc) weakly coordinated to phosphorus and hard‐ligand donors (carboxylates, imidazolates, alkoxylates).…”