Synthesis of Square Planar Cu 4 Clusters Osei, Manasseh Kusi; Mirzaei, Saber; Bogetti, Xiaowei ...
Angewandte Chemie International Edition,
10/2022, Letnik:
61, Številka:
41
Journal Article
Recenzirano
Abstract
Template‐assisted synthesis of well‐defined polynuclear clusters remains a challenge for M
4
square planar topologies. Herein, we present a tetraamine scaffold
R
L(NH
2
)
4
, where L is a ...rigidified resorcin4arene, to direct the formation of
C
4
‐symmetric
R
L(NH)
4
Cu
4
clusters with Cu−Cu distances around 2.7 Å, suggesting metal‐metal direct interactions are operative since the sum of copper's van der Waals radii is 2.8 Å. DFT calculations display HOMO to HOMO‐3 residing all within a 0.1 eV gap. These four orbitals display significant electron density contribution from the Cu centers suggesting a delocalized electronic structure. The one‐electron oxidized Cu
4
+
species was probed by variable temperature X‐band continuous wave‐electron paramagnetic resonance (CW‐EPR), which displays a multiline spectrum at room temperature. This work presents a novel synthetic strategy for M
4
clusters and a new platform to investigate activation of small molecules.
This study explores a new mode of contortion in perylene diimides where the molecule is bent, like a bow, along its long axis. These bowed PDIs were synthesized through a facile fourfold Suzuki ...macrocyclization with aromatic linkers and a tetraborylated perylene diimide that introduces strain and results in a bowed structure. By altering the strings of the bow, the degree of bending can be controlled from flat to highly bent. Through spectroscopy and quantum chemical calculations, it is demonstrated that the energy of the lowest unoccupied orbital can be controlled by the degree of bending in the structures and that the energy of the highest occupied orbital can be controlled to a large extent by the constitution of the aromatic linkers. The important finding is that the bowing results not only in red-shifted absorptions but also more facile reductions.
We report the synthesis of a bilayer chiral nanographene incorporating a 7helicene scaffold and two perylene-diimide (PDI) subunits. Twofold visible-light-induced oxidative cyclization of a ...phenanthrene framework selects for the desired PDI-helicene, despite the immense strain that distinguishes this helicene from two other accessible isomers. This strain arises from the extensive intramolecular overlap of the PDI subunits, which precludes racemization, even at elevated temperatures. Relative to a smaller homologue, this PDI-helicene exhibits amplified electronic circular dichroism. It also readily and reversibly accepts four electrons electrochemically. Modifications to the core phenanthrene subunit change the fluorescence and electrochemistry of the PDI-helicene without significantly impacting its electronic circular dichroism or UV-visible absorbance.
Visible-light-induced oxidative cyclization of a phenanthrene framework overcomes immense strain to yield a bilayer perylene-diimide helicene.
We report the synthesis of a bilayer chiral nanographene incorporating a 7helicene scaffold and two perylene-diimide (PDI) subunits. Twofold visible-light-induced oxidative cyclization of a ...phenanthrene framework selects for the desired PDI-helicene, despite the immense strain that distinguishes this helicene from two other accessible isomers. This strain arises from the extensive intramolecular overlap of the PDI subunits, which precludes racemization, even at elevated temperatures. Relative to a smaller homologue, this PDI-helicene exhibits amplified electronic circular dichroism. It also readily and reversibly accepts four electrons electrochemically. Modifications to the core phenanthrene subunit change the fluorescence and electrochemistry of the PDI-helicene without significantly impacting its electronic circular dichroism or UV-visible absorbance.
Visible-light-induced oxidative cyclization of a phenanthrene framework overcomes immense strain to yield a bilayer perylene-diimide helicene.
We report the synthesis of a bilayer chiral nanographene ...incorporating a 7helicene scaffold and two perylene-diimide (PDI) subunits. Twofold visible-light-induced oxidative cyclization of a phenanthrene framework selects for the desired PDI-helicene, despite the immense strain that distinguishes this helicene from two other accessible isomers. This strain arises from the extensive intramolecular overlap of the PDI subunits, which precludes racemization, even at elevated temperatures. Relative to a smaller homologue, this PDI-helicene exhibits amplified electronic circular dichroism. It also readily and reversibly accepts four electrons electrochemically. Modifications to the core phenanthrene subunit change the fluorescence and electrochemistry of the PDI-helicene without significantly impacting its electronic circular dichroism or UV-visible absorbance.
Abstract Polycystic kidney disease (PKD), a disease characterized by enlargement of the kidney through cystic growth is the fourth leading cause of end-stage kidney disease world-wide. TRPV4, a ...calcium-permeable TRP, channel participates in kidney cell physiology and since TRPV4 forms complexes with another channel whose malfunction is associated to PKD, TRPP2 (or PKD2), we sought to determine whether patients with PKD, exhibit previously unknown mutations in TRPV4. Here, we report the presence of mutations in the TRPV4 gene in patients diagnosed with PKD and determine that they produce gain-of-function (GOF). Mutations in the sequence of the TRPV4 gene have been associated to a broad spectrum of neuropathies and skeletal dysplasias but not PKD, and their biophysical effects on channel function have not been elucidated. We identified and examined the functional behavior of a novel E6K mutant and of the previously known S94L and A217S mutant TRVP4 channels. The A217S mutation has been associated to mixed neuropathy and/or skeletal dysplasia phenotypes, however, the PKD carriers of these variants had not been diagnosed with these reported clinical manifestations. The presence of certain mutations in TRPV4 may influence the progression and severity of PKD through GOF mechanisms. PKD patients carrying TRVP4 mutations are putatively more likely to require dialysis or renal transplant as compared to those without these mutations.
Here we examine a family of trinuclear iron complexes by multiple-wavelength, anomalous diffraction (MAD) to explore the redox load distribution within cluster materials by the free refinement of ...atomic scattering factors. Several effects were explored that can impact atomic scattering factors within clusters, including 1) metal atom primary coordination sphere, 2) M–M bonding, and 3) redox delocalization in formally mixed-valent species. Complexes were investigated which vary from highly symmetric to fully asymmetric by 57Fe Mössbauer and X-ray diffraction to explore the relationship between MAD-derived data and the data available from these widely used characterization techniques. The compounds examined include the all-ferrous clusters nBu4N(tbsL)Fe3(μ3–Cl) (1) (tbsL6– = 1,3,5-C6H9(NC6H4-o-NSitBuMe2)36–), (tbsL)Fe3(py) (2), K(C222)2(tbsL)Fe3(μ3–NPh) (4) (C222 = 2,2,2-cryptand), and the mixed-valent (tbsL)Fe3(μ3–NPh) (3). Redox delocalization in mixed-valent 3 was explored with cyclic voltammetry (CV), zero-field 57Fe Mössbauer, near-infrared (NIR) spectroscopy, and X-ray crystallography techniques. We find that the MAD results show an excellent correspondence to 57Fe Mössbauer data; yet also can distinguish between subtle changes in local coordination geometries where Mössbauer cannot. Differences within aggregate oxidation levels are evident by systematic shifts of scattering factor envelopes to increasingly higher energies. However, distinguishing local oxidation levels in iso- or mixed-valent materials can be dramatically obscured by the degree of covalent intracore bonding. MAD-derived atomic scattering factor data emphasize in-edge features that are often difficult to analyze by X-ray absorption near edge spectroscopy (XANES). Thus, relative oxidation levels within the cluster were most reliably ascertained from comparing the entire envelope of the atomic scattering factor data.
Using ammonia as a clean hydrogen storage medium, and subsequent utilization as an energy source, requires an understanding of the multi‐electron ammonia oxidation half‐reaction. As described in ...their communication on page 11479 ff., Ménard et al. have devised a full synthetic cycle for ammonia oxidation using an abundant salen‐based Mn catalyst. These results may contribute to the development of a fully catalytic system for ammonia oxidation chemistry.