Rational Design of a 3D MnII‐Metal–Organic Framework Based on a Nonmetallated Porphyrin Linker for Selective Capture of CO2 and One‐Pot Synthesis of Styrene Carbonates. Issue 62 (17th October 2018)

• Record Type: Journal Article
• Authors: Sharma, Nayuesh; Dhankhar, Sandeep Singh; Kumar, Sandeep; Kumar, T. J. Dhilip; Nagaraja, C. Mallaiah
• Is Part Of: Chemistry. Volume 24:Issue 62(2018)
• Page Start: 16662
• Page End: 16669
• Publication Date: 2018-10-17
• Subjects: heterogeneous catalysis -- metal–organic frameworks -- one-pot synthesis -- porphyrin linkers -- selective CO2 storage; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201803842
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: A 3D Mn II ‐porphyrin metal–organic framework (MOF), [{Mn2 (TCPP)⋅ 2H2 O}⋅ DMF] n (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 2 and 4.66×4.93 Å 2 running along the crystallographic a axis. Owing to the presence of a nonmetallated porphyrin cavity, MOF1 exhibits selective storage of CO2 with an isosteric heat of adsorption value of 32.1 kJ mol −1, which is further supported by theoretical calculations with the calculated binding energy (BE) of 29.78 kJ mol −1 . Interestingly, the nonmetallated nature of the porphyrin ligand was exploited for implantation of coordinatively unsaturated Fe III ions to generate a Fe III @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 CO2 was also achieved using Fe III @MOF1 as a catalyst. The rational design of a porous Mn II ‐porphyrin MOF for the selective capture of CO2 and the one‐pot synthesis of styrene carbonates at mild conditions is reported. Abstract : Catch and kill : A Mn II ‐porphyrin metal–organic framework MOF1 was constructed; it exhibits an interesting 3D framework structure with two types of 1D channels and shows selective adsorption of CO2 . The nonmetallated nature of the porphyrin ligand was used to implant Fe III ions to generate a Fe@MOF1 framework which acts as an efficient recyclable catalyst for the oxidation of styrenes and for the one‐pot synthesis of styrene carbonates (see figure).