The chemistry of metal–organic frameworks (MOFs), a new
class of emerging crystalline porous solids with three-dimensional
(3D) networks composed of metals and multidentate organic molecules,
was introduced by using three differently shaped crystals. We reported
new and mild MOF synthesis methods that are simple and devised to
be performed in high school or primarily undergraduate school settings.
MOF applications were demonstrated by use of our synthesized MOFs
in the capture of iodine as a potentially hazardous molecule from
solution and as a drug delivery system. These applications can be
visually confirmed in minutes. Students can gain knowledge on advanced
topics, such as drug delivery systems, through these easy-to-prepare
MOFs. Furthermore, students can gain an understanding of powder X-ray
analysis and ultraviolet–visible near-infrared spectroscopy.
This laboratory experience is practical, including synthesis and application
of MOFs. The entire experiment has also been recorded as an educational
video posted on YouTube as a free public medium for students to watch
and learn. In this paper we first report the steps we took to synthesize
and analyze the MOFs, followed by a description of a simple demonstration
that we verified to effectively exhibit adsorption by MOFs. We conclude
with a description of how the laboratory activity and demonstration
were implemented in an undergraduate chemistry laboratory.
A new covalent organic framework (COF) based on imine bonds was assembled from 2-(4-formylphenyl)-5-formylpyridine and 1,3,6,8-tetrakis(4-aminophenyl)pyrene, which showed an interesting dual-pore structure with high crystallinity. Postmetallation of the COF with Pt occurred selectively at the N donor (imine and pyridyl) in the larger pores. The metallated COF served as an excellent recyclable heterogeneous photocatalyst for decarboxylative difluoroalkylation and oxidative cyclization reactions.
Herein, the synthesis and characterization of a series of heteroleptic cycloplatinated(II) complexes [Pt(p-MeC 6 H 4 )(dfppy)(L)], dfppy = 2-(2,4-difluorophenyl)pyridinate), with different para-substituted triphenylphosphine ligands (L) are reported. The complexes exhibit greenish-blue phosphorescence under UV light at room temperature in their solid states. Their emissions appear as structured bands which indicates that the emissions mainly originate from the elec-tronic transitions in the dfppy ligand with small contribution of metal to ligand and/or ligand to ligand charge transfers. The phosphine ligands do not have a considerable impact on the shape and wavelength of the emissions. However, the electron density of the phosphine ligands affects the emission strengths significantly. To rationalize the experimental photophysical data, density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations were employed for all the complexes.
The
field of photodynamic therapy (PDT) has continued to show promise
as a potential method for treating tumors. In this work, a photosensitizer
(PS) has been delivered to cancer cell lines for PDT by incorporation
into the metal–organic framework (MOF) as an organic linker.
By functionalizing the surface of MOF nanoparticles with maltotriose,
the PS can efficiently target cancer cells with preferential uptake
into pancreatic and breast cancer cell lines. Effective targeting
overcomes some current problems with PDT including long-term photosensitivity
and tumor specificity. Developing a PS with optimal absorption and
stability is one of the foremost challenges in PDT, and the synthesis
of a chlorin, which is activated by long wavelength light and is resistant
to photobleaching, is described. This chlorin-based MOF shows anticancer
ability several times higher than that of porphyrin-based MOFs with
little toxicity to normal cell lines and no dark toxicity.
Two-dimensional urea- and thiourea-containing covalent organic
frameworks (COFs) were synthesized at ambient conditions at large
scale within 1 h in the absence of an acid catalyst. The site-isolated
urea and thiourea in the COF showed enhanced catalytic efficiency
as a hydrogen-bond-donating organocatalyst compared to the molecular
counterparts in epoxide ring-opening reaction, aldehyde acetalization,
and Friedel–Crafts reaction. The COF catalysts also had excellent
recyclability.
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