Microporous Metal-organic Material Research Articles

Synthesis of porphyrin@MOFs type catalysts through “one-pot” self-assembly

Reaction of 1,1-bis-[3,5-bis(carboxy) phenoxy]methane (H4L) and CuCl2 in the presence of meso-tetrakis[4-(nicotinoyloxy)phenyl]porphyrin (TNPP) and manganese complex of TNPP (MnTNPP), respectively, under solvothermal condition afforded CuTNPP@MOF and MnTNPP@MOF, microporous metal-organic materials containing neutral CuTNPP or MnTNPP molecules in their frameworks. The nitrogen sorption isotherm measurement, ultraviolet visible adsorption spectroscopy (UV–vis), powder X-ray diffraction (XRD), and thermogravimetric analysis (TGA) characterizations showed that CuTNPP@MOF and MnTNPP@MOF were permanently porous and had heterogeneous catalytic activity for the oxidation of 3,5-di-tert-butylcatechol.

Stepwise Transformation of the Molecular Building Blocks in a Porphyrin-Encapsulating Metal–Organic Material

When immersed in solutions containing Cu(II) cations, the microporous metal-organic material P11 ([Cd4(BPT)4]·[Cd(C44H36N8)(S)]·[S], BPT = biphenyl-3,4',5-tricarboxylate) undergoes a transformation of its [Cd2(COO)6](2-) molecular building blocks (MBBs) into novel tetranuclear [Cu4X2(COO)6(S)2] MBBs to form P11-Cu. The transformation occurs in single-crystal to single-crystal fashion, and its stepwise mechanism was studied by varying the Cd(2+)/Cu(2+) ratio of the solution in which crystals of P11 were immersed. P11-16/1 (Cd in framework retained, Cd in encapsulated porphyrins exchanged) and other intermediate phases were thereby isolated and structurally characterized. P11-16/1 and P11-Cu retain the microporosity of P11, and the relatively larger MBBs in P11-Cu permit a 20% unit cell expansion and afford a higher surface area and a larger pore size.

Post‐Synthetic Modification of Porphyrin‐Encapsulating Metal–Organic Materials by Cooperative Addition of Inorganic Salts to Enhance CO2/CH4 Selectivity

Keeping MOM: Reaction of biphenyl-3,4',5-tricarboxylate and Cd(NO3)2 in the presence of meso-tetra(N-methyl-4-pyridyl)porphine tetratosylate afforded porph@MOM-11, a microporous metal–organic material (MOM) that encapsulates cationic porphyrins and solvent in alternating open channels. Porph@MOM-11 has cation and anion binding sites that facilitate cooperative addition of inorganic salts (such as M+Cl-) in a stoichiometric fashion.

Templated Synthesis, Postsynthetic Metal Exchange, and Properties of a Porphyrin-Encapsulating Metal–Organic Material

Reaction of biphenyl-3,4',5-tricarboxylate (H(3)BPT) and CdCl(2) in the presence of meso-tetra(N-methyl-4-pyridyl)porphine tetratosylate (TMPyP) afforded porph@MOM-10, a microporous metal-organic material containing CdTMPyP cations encapsulated in an anionic Cd(II) carboxylate framework, [Cd(6)(BPT)(4)Cl(4)(H(2)O)(4)]. Porph@MOM-10 is a versatile platform that undergoes exchange to serve as the parent of a series of porph@MOMs that exhibit permanent porosity and heterogeneous catalytic activity.

Microporous metal organic materials: promising candidates as sorbents for hydrogen storage.

Advancement in hydrogen storage techniques represents one of the most important areas of today's materials research. While extensive efforts have been made to the existing techniques, there is no viable storage technology capable of meeting the DOE cost and performance targets at the present time. New materials with significantly improved hydrogen adsorption capability are needed. Microporous metal coordination materials (MMOM) are promising candidates for use as sorbents in hydrogen adsorption. These materials possess physical characteristics similar to those of single-walled carbon nanotubes (SWNTs) but also exhibit a number of improved features. Here, we report a novel MMOM structure and its room-temperature hydrogen adsorption properties.