Porphyrin and phthalocyanine-based metal organic frameworks beyond metal-carboxylates

De, Siddhartha; Devic, Thomas; Fateeva, Alexandra

doi:10.1039/d0dt03903a

Cited by 39 publications

(33 citation statements)

References 158 publications

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“…The recent achievements and progress in the field of porphyrin-based MOFs for biomedical applications were published by Chen et al 14 Moreover, another review dealing with porphyrin and phthalocyanine metal−organic frameworks, their synthesis, structure, and topology was reported recently. 15 As has been stated above, in the past 10 years, there has been a growing interest in metal−metalloporphyrin frameworks. The mentioned interest is evident from Figure 1, where results of the search in the Scopus database using the phrase "metal−organic frameworks and porphyrin" are summarized.…”

Section: ■ Introductionmentioning

confidence: 93%

Novel Lanthanide(III) Porphyrin-Based Metal–Organic Frameworks: Structure, Gas Adsorption, and Magnetic Properties

et al. 2021

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The present work focuses on the hydrothermal synthesis and properties of porous coordination polymers of metal–porphyrin framework (MPF) type, namely, {[Pr4(H2TPPS)3]·11H2O} n (UPJS-10), {[Eu/Sm(H2TPPS)]·H3O+·16H2O} n (UPJS-11), and {[Ce4(H2TPPS)3]·11H2O} n (UPJS-12) (H2TPPS = 4,4′,4″,4‴-(porphyrin-5,10,15,20-tetrayl)tetrakisbenzenesulfonate(4-)). The compounds were characterized using several analytical techniques: infrared spectroscopy, thermogravimetric measurements, elemental analysis, gas adsorption measurements, and single-crystal structure analysis (SXRD). The results of SXRD revealed a three-dimensional open porous framework containing crossing cavities propagating along all crystallographic axes. Coordination of H2TPPS4– ligands with Ln(III) ions leads to the formation of 1D polymeric chains propagating along the c crystallographic axis. Argon sorption measurements at −186 °C show that the activated MPFs have apparent BET surface areas of 260 m2 g–1 (UPJS-10) and 230 m2 g–1 (UPJS-12). Carbon dioxide adsorption isotherms at 0 °C show adsorption capacities up to 1 bar of 9.8 wt % for UPJS-10 and 8.6 wt % for UPJS-12. At a temperature of 20 °C, the respective CO2 adsorption capacities decreased to 6.95 and 5.99 wt %, respectively. The magnetic properties of UPJS-10 are characterized by the presence of a close-lying nonmagnetic ground singlet and excited doublet states in the electronic spectrum of Pr(III) ions. A much larger energy difference was suggested between the two lowest Kramers doublets of Ce(III) ions in UPJS-12. Finally, the analysis of X-band EPR spectra revealed the presence of radical spins, which were tentatively assigned to be originating from the porphyrin ligands.

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Section: ■ Introductionmentioning

confidence: 93%

Novel Lanthanide(III) Porphyrin-Based Metal–Organic Frameworks: Structure, Gas Adsorption, and Magnetic Properties

et al. 2021

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“…Porphyrins and metalloporphyrins as such are well known to exhibit photocatalytic antimicrobial properties. , Their incorporations as building blocks for the preparation of both 2D and 3D frameworks are also well documented and the various synthetic methodologies have recently been thoroughly reviewed (COFs , and MOFs , ). For instance, the construction of 3D COFs may proceed upon condensing tetrahedral and quadrilateral building blocks such as a tetrafunctionalized porphyrin unit under solvothermal conditions (Figure , left), whereas the design of 2D COFs proceeds with a linear building block (Figure , right).…”

Section: Mof and Cof Designs And Related Propertiesmentioning

confidence: 99%

Porphyrin-Containing MOFs and COFs as Heterogeneous Photosensitizers for Singlet Oxygen-Based Antimicrobial Nanodevices

Schlachter

Asselin

Harvey

2021

ACS Appl. Mater. Interfaces

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Visible-light irradiation of porphyrin and metalloporphyrin dyes in the presence of molecular oxygen can result in the photocatalytic generation of singlet oxygen (1O2). This type II reactive oxygen species (ROS) finds many applications where the dye, also called the photosensitizer, is dissolved (i.e., homogeneous phase) along with the substrate to be oxidized. In contrast, metal–organic frameworks (MOFs) are insoluble (or will disassemble) when placed in a solvent. When stable as a suspension, MOFs adsorb a large amount of O2 and photocatalytically generate 1O2 in a heterogeneous process efficiently. Considering the immense surface area and great capacity for gas adsorption of MOFs, they seem ideal candidates for this application. Very recently, covalent–organic frameworks (COFs), variants where reticulation relies on covalent rather than coordination bonds, have emerged as efficient photosensitizers. This comprehensive mini review describes recent developments in the use of porphyrin-based or porphyrin-containing MOFs and COFs, including nanosized versions, as heterogeneous photosensitizers of singlet oxygen toward antimicrobial applications.

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“…The occurrence of inter- or intramolecular metal-to-ligand interactions is dictated by the interdeck distance depending on the size of lanthanide ions. These observations might be important for a rational selection of the most appropriate binding motives for creating conductive Pc-based 2D and 3D MOFs, which are currently among the most intensely explored systems in the MOF-related studies. ,, The electric properties of the intermolecular 1D assemblies make it possible to use technologically feasible methods for their controlled alignment on surfaces under an applied electric field. Another important advantage of these as-formed assemblies over conventional covalently linked conjugated polymers is that the comparative weakness of their bonding becomes their strength in utilization and recycling.…”

Section: Discussionmentioning

confidence: 99%

Ion-Driven Self-Assembly of Lanthanide Bis-phthalocyaninates into Conductive Quasi-MOF Nanowires: an Approach toward Easily Recyclable Organic Electronics

et al. 2021

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Controlled self-assembly and rapid disintegration of supramolecular nanowires is potentially useful for ecology-friendly organic electronics. Herein, a novel method exploiting the binding between crown-substituted double-decker lanthanide phthalocyaninates (ML2, M = Lu, Ce, Tb) and K+ ions is applied for the one-step fabrication of macroscopically long conductive one-dimensional quasi-metal–organic frameworks. Their properties are controlled by the size of the lanthanide ion guiding the assembly through either intra- or intermolecular interactions. A LuL2 linker with a small interdeck distance yields fully conjugated intermolecular-bonded K+–LuL2 nanowires with a thickness of 10–50 nm, a length of up to 50 μm, and a conductivity of up to 11.4 S cm–1, the highest among them being reported for phthalocyanine assemblies. The large size of CeL2 and TbL2 leads to the formation of mixed intra- and intermolecular K+–ML2 phases with poor electric properties. A field-assisted method is developed to deposit aligned conductive K+–LuL2 assemblies on solids. The solid-supported nanowires can be disintegrated into starting components in a good aprotic solvent for further recycling.

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Porphyrin and phthalocyanine-based metal organic frameworks beyond metal-carboxylates

Abstract: The recently emerging class of MOFs based on porphyrins and phthalocyanines bearing alternative coordinating groups offers opportunities for functional materials.

Cited by 39 publications

References 158 publications

Novel Lanthanide(III) Porphyrin-Based Metal–Organic Frameworks: Structure, Gas Adsorption, and Magnetic Properties

Novel Lanthanide(III) Porphyrin-Based Metal–Organic Frameworks: Structure, Gas Adsorption, and Magnetic Properties

Porphyrin-Containing MOFs and COFs as Heterogeneous Photosensitizers for Singlet Oxygen-Based Antimicrobial Nanodevices

Ion-Driven Self-Assembly of Lanthanide Bis-phthalocyaninates into Conductive Quasi-MOF Nanowires: an Approach toward Easily Recyclable Organic Electronics

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