Rational Design of a 3D Mn^II‐Metal–Organic Framework Based on a Nonmetallated Porphyrin Linker for Selective Capture of CO₂ and One‐Pot Synthesis of Styrene Carbonates

Abstract

A 3D Mn -porphyrin metal-organic framework (MOF), [{Mn (TCPP)⋅2H O}⋅DMF] (MOF1) (TCPP=5,10,15,20-tetrakis(4-benzoate)porphyrin), was constructed; it exhibits an interesting 3D framework structure with two types of 1D channels of dimensions of 3.94×8.37 Å and 4.66×4.93 Å running along the crystallographic a axis. Owing to the presence of a nonmetallated porphyrin cavity, MOF1 exhibits selective storage of CO with an isosteric heat of adsorption value of 32.1 kJ mol , which is further supported by theoretical calculations with the calculated binding energy (BE) of 29.78 kJ mol . Interestingly, the nonmetallated nature of the porphyrin ligand was exploited for implantation of coordinatively unsaturated Fe ions to generate a Fe @MOF1 framework, which acts as an efficient recyclable catalyst for the oxidation of styrenes to the corresponding epoxides in the presence of PhIO as an oxidant at room temperature. Moreover, the one-pot synthesis of styrene carbonates from styrenes and CO was also achieved using Fe @MOF1 as a catalyst. The rational design of a porous Mn -porphyrin MOF for the selective capture of CO and the one-pot synthesis of styrene carbonates at mild conditions is reported.

A Novel Cerium(IV)‐Based Metal‐Organic Framework for CO2 Chemical Fixation and Photocatalytic Overall Water Splitting

“…Based on these results and some literature reports, [21][22][23] a possible radical pathway involved mechanism in our case was proposed and depicted in Scheme 1. First, open Ce 4 + sites of CSUST-3 react with TBHP to produce Ce 5 + -peroxy adducts, which next release t-butoxy radicals and regenerate Ce 4 + sites.…”

“…The slightly lower efficiencies gave by 4-chlorostyrene and 4-methylstyrene are consistent with the trend reported in literature. [21,23] When 4-tert-butylstyrene with a bulky tert-butyl group used, lower yield (36 %) were obtained, which may be due to the size effect of MOF catalysis.…”

“…MOFs, due to their compositions and functionalities can be easily tunable, they are particularly desirable for such tandem reactions [18–20] . Commonly, through incorporating two types of catalytical active sites (one for olefin epoxidation and another for epoxide‐CO 2 cycloaddition) can realize MOFs for one‐pot conversion of olefins into cyclic organic carbonates [21–23] . However, in most cases, the synergistic catalysis from different catalytic sites is not easy to control, thus development of MOFs with only one type of catalytic center, which can simultaneously promote the two consecutive steps, are ideal choices, but are very rarely been reported.…”

Oxidative carboxylation of olefins with CO2: environmentally benign access to five-membered cyclic carbonates

“…35 Inspired by these works, Nagaraja and coworkers synthesized a novel Mn(II)-porphyrin metal-organic framework, [{Mn 2 (TCPP)$2H 2 O}$DMF]n (MOF1) through the reaction of Mn(NO 3 ) 2 $6H 2 O and H 4 TCPP ligand under the solvothermal conditions. 36 Single crystal X-ray structural determination revealed that MOF1 crystallizes in the monoclinic crystal system with a centrosymmetric P2 1 /n space group and features a 3D architecture constituted by binuclear Mn(II) nodes and non-metallated porphyrin ligand. Interestingly, the nonmetallated nature of porphyrin ring was exploited for the implantation of Lewis acidic Fe(III) ions to generate Fe(III) @MOF1 material.…”

Alkyl‐Linked Porphyrin Porous Polymers for Gas Capture and Precious Metal Adsorption

“…[ 9,13–15 ] Recent studies that focus on this feature include porphyrin‐based conjugated microporous polymers (CMPs) with azide groups, [ 16 ] a porphyrin‐ and pyrene‐based CMP (Por–Py–CMP), [ 14 ] a triazine‐functionalized porphyrin‐based porous organic polymer (TPOP‐1), [ 17 ] and 3D Mn II ‐porphyrin metal–organic framework (MOF). [ 18 ] Porphyrin‐based porous structures also show ability to store hydrogen (H 2 ) gas. [ 13,19,20 ] Polyporphyrins with high surface areas (e.g., over 1500 m 2 g −1 ) and functionalized with thiophenyl groups showed 5% mass increase after H 2 adsorption at 77 K and 65 bar.…”