Metal–Organic Frameworks: Porphyrinic Frameworks

Abstract

There has been growing interest in coordination chemistry, particularly in the field of porous metal–organic frameworks (MOFs). Since the functionalities of MOFs can be systematically tuned by integrating functional groups in their frameworks, MOF materials have been realized applications in a number of fields, including luminescence, gas storage, sensing, magnetics, and catalysis. Because porphyrins and metalloporphyrins have rigid structures and remarkable functionalities of catalysis, charge, and energy transformations, they have been used as functional building blocks to fabricate porphyrinic MOFs for applications in various fields. This chapter is focused on recent progress on the emerging functional materials, including synthetic strategies and applications of porphyrinic MOFs.

In Situ Porphyrin Substitution in a Zr(IV)‐MOF for Stability Enhancement and Photocatalytic CO2 Reduction

“…[42] Replacing the labile NDIDB 2− ligand in BUT-109(Zr) to a robust one may strengthen the framework structure and deliver a new functional MOF. Given the structural rigidity and multifunctional feature of porphyrins, as well as the matching molecular size and geometry with NDIDB 2− , a di-carboxylic acid porphyrin ligand 4,4'-(porphyrin-5,15-diyl) dibenzoic acid (H 2 DCPP) [43] (Figure S1, Supporting Information) was selected as the competing ligand to substitute NDIDB 2− in BUT-109(Zr) (Figure 1a). Subsequently, the H 2 DCPP substitution reaction for a stable and versatile MOF was conducted by modifying BUT-109(Zr) in different ways (Figures 1b and 2).…”

“…[53] Porphyrin shows excellent lightharvesting ability, and the ordered structure of porphyrin-based MOFs can distribute these units uniformly in space, further improving their catalytic efficiency. [43,[54][55][56][57][58][59] Hence, porphyrin-MOFs represents a promising class of heterogenous photocatalysts. Jiang and co-workers have demonstrated that PCN-222 can selectively capture and convert CO 2 to HCOO − anion with high efficiency under visible-light irradiation.…”