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

Abstract

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.

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

“…The partial exchange of framework Cd atoms by Mn is in accord with our earlier observation. [4] However, there is no metal exchange with respect to the Cd porphyrins as verified by crystallographic refinement and solution-state UV/Vis spectroscopy (Figure S7).…”

“…Chloride anions replaced the axially coordinated solvent molecules with a CdÀ Cl bonds of 2.555(8) that is consistent with reported values. [4] As shown in Table 1, Cd1 paddlewheels bind sodium cations over two equivalent binding sites through coordination to two carboxylate oxygen atoms ( Figure S5 and S6) whereas Cd2 paddlewheels do not bind to sodium cations. The NaÀO(carboxylate) distances of 2.344(17) and 2.495 (18) are within the range that would be expected (see Supporting Information).…”

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Porous metal-organic materials (MOMs) that incorporate porphyrins can combine the physicochemical properties of the porphyrin [1, 2] while retaining the permanent porosity [3] of the MOM, thereby facilitating gas storage, [4] separations, [5] and luminescence. [6] There are two established approaches to incorporate porphyrins into MOMs: the use of functionalized porphyrins as nodes or linkers, [7] porphMOMs; selective encapsulation of porphyrins into cages, porph@MOMs.

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“…[4,10] That porph@MOMs are now readily available affords an opportunity to fine-tune their structure and properties through either pre-synthetic design or post-synthetic modification (PSM). [11,12] PSM typically involves condensation [11] or coordination chemistry [12] and in effect turns MOMs that are amenable to PSM into platforms for the study of structurefunction relationships.…”

“…[4] Although rtl has the same point symbol {4.6 2 } 2 {4 2 .6 10 .8 3 } as zzz, rtl and zzz exhibit different connectivity. Figure S2 reveals how the eight-membered rings adopt 1,3-alternate geometry in zzz whereas they exhibit 1,2-alternate geometry in rtl.…”