2D Porphyrinic Metal-Organic Frameworks Featuring Rod-Shaped Secondary Building Units

Abstract

Metal-organic frameworks (MOFs) encompass a rapidly expanding class of materials with diverse potential applications including gas storage, molecular separation, sensing and catalysis. So-called ‘rod MOFs’, which comprise infinitely extended 1D secondary building units (SBUs), represent an underexplored subclass of MOF. Further, porphyrins are considered privileged ligands for MOF synthesis due to their tunable redox and photophysical properties. In this study, the CuII complex of 5,15-bis(4-carboxyphenyl)-10,20-diphenylporphyrin (H2L-CuII, where H2 refers to the ligand’s carboxyl H atoms) is used to prepare two new 2D porphyrinic rod MOFs PROD-1 and PROD-2. Single-crystal X-ray analysis reveals that these frameworks feature 1D MnII- or CoII-based rod-like SBUs that are coordinated by labile solvent molecules and photoactive porphyrin moieties. Both materials were characterised using infrared (IR) spectroscopy, powder X-ray diffraction (PXRD) spectroscopy and thermogravimetric analysis (TGA). The structural attributes of PROD-1 and PROD-2 render them promising materials for future photocatalytic investigations.

Dynamic Responsive Cd-MOF upon the Stimulation of Temperature and Solvent for Photocatalytic CO2RR

“…As shown in Figure S9, the conjugated moiety, [Cd 2 (BA)­(Im)] formed by the imidazole ring in BMB, the benzoate fragment in L 3– , and the Cd center is beneficial to capture photographs and generate photoelectrons. Photoelectrons can be transferred quickly through rod SBUs, thus realizing the effective separation of photoelectron-hole pairs. − Compared with BMB and H 3 L ligands, the PL peak and fluorescence lifetime of AQNU-5 were decreased to some extent, which indicates the rapid separation of photoelectron-hole pairs and the accumulation of long-lived electrons − (Figures S14 and S15). Apart from this, twisting of methylene groups in BMB and H 3 L, as well as rocking of rod SBUs, promote the cleavage of Cd–N and Cd–O to generate active sites.…”

Self-Organization of Porphyrin–POM Dyads: Nonplanar Diacids and Oxoanions in Low-Dimensional H-Bonding Networks

“…Porphyrin involvement in crystal engineering—using crystal organizational principles to engender a desired solid state or set of properties—is usually the domain of metalloporphyrins, owing to the macrocycle’s well-known metal chelation [ 10 ]. Metalloporphyrins are among the earliest examples of rationally designed coordination polymers [ 11 , 12 ], providing ‘open’ axial metal coordination sites in porous materials; these compounds are principally constructed from meso-4-carboxyphenyl- and -4-pyridylporphyrins and closely related ligands [ 13 ]. Aside from rationally designed materials, the organization of planar porphyrin compounds in the solid state is similar to that of other mostly planar organic molecules, with usual edge-to-face and face-to-face aromatic stacking predominating in lieu of hydrogen bonding [ 14 , 15 , 16 ].…”

Construction of Two Stable Co(II)-Based Hydrogen-Bonded Organic Frameworks as a Luminescent Probe for Recognition of Fe3+ and Cr2O72− in H2O

“…HOFs have attracted a significant deal of attention especially because of their broad applications, ranging from chemical sensing [ 6 ] and bioimaging [ 7 , 8 ] to lighting [ 9 ] and 3D optical storage [ 10 , 11 ]. The metal-organic frameworks (MOFs) and covalent-organic frameworks (COFs) are usually connected by coordination bonds or covalent bonds between atoms and show relatively high stabilities [ 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 ], while the HOFs are linked by weak non-covalent interactions, such as hydrogen bonds and π−π stacking interactions, and exhibit relatively low stabilities [ 21 , 22 , 23 , 24 , 25 ]. For HOFs, the solvent guests play important roles in the construction of the supermolecular network system.…”