Probing the structure of Copper(II)-Casiopeina type coordination complexes [Cu(O-O)(N-N)]+ by EPR and ENDOR spectroscopy

Folli, Andrea; Ritterskamp, Nadine; Richards, Emma; Platts, James Alexis; Murphy, D. M.

doi:10.1016/j.jcat.2020.07.016

Cited by 7 publications

(4 citation statements)

References 61 publications

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“…NQR studies on pyridyl adducts with Lewis acids (LA) confirm the largest component to be along the direction of the lone pair of electrons at the 14 N atom, i.e., along the N…LA axis. [31] This has been confirmed in Cu…pyridyl complexes studied by orientation-selective ENDOR, [32][33][34][35][36] and is what we observe here for MFM-520(Zn 0.995 Cu 0.005 ). However, the |e 2 Qq/h| value here is larger than that typically observed in Cu•••pyridyl complexes (typically −2.5 to −3 MHz; Table 1).…”

Section: Endor Spectrasupporting

confidence: 85%

Analysis of a Cu‐Doped Metal–Organic Framework, MFM‐520(Zn_1‐xCu_x), for NO₂ Adsorption

Wang,

Sheveleva,

et al. 2023

Advanced Science

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MFM‐520(Zn) confines dimers of NO2 with a high adsorption of 4.52 mmol g−1 at 1 bar at 298 K. The synthesis and the incommensurate structure of Cu‐doped MFM‐520(Zn) are reported. The introduction of paramagnetic Cu2+ sites allows investigation of the electronic and geometric structure of metal site by in situ electron paramagnetic resonance (EPR) spectroscopy upon adsorption of NO2. By combining continuous wave and electron‐nuclear double resonance spectroscopy, an unusual reverse Berry distorted coordination geometry of the Cu2+ centers is observed. Interestingly, Cu‐doped MFM‐520(Zn0.95Cu0.05) shows enhanced adsorption of NO2 of 5.02 mmol g−1 at 1 bar at 298 K. Whereas MFM‐520(Zn) confines adsorbed NO2 as N2O4, the presence of monomeric NO2 at low temperature suggests that doping with Cu2+ centers into the framework plays an important role in tuning the dimerization of NO2 molecules in the pore via the formation of specific host‐guest interactions.

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Section: Endor Spectrasupporting

confidence: 85%

Analysis of a Cu‐Doped Metal–Organic Framework, MFM‐520(Zn_1‐xCu_x), for NO₂ Adsorption

Wang,

Sheveleva,

et al. 2023

Advanced Science

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“…All the derivatives showed to be open shell species due to the presence of the copper atom in oxidation state +2, therefore in all the cases the last electron is localized on a SOMO (single occupied molecular orbital) which is the one considered in the achievement of the electronic gap. The original geometry is expected to be a planar square (D 2 h) as it is normally found in this kind of compounds, [19,20] however in the present case the −NO 3 group that could be considered as a counterion actually participates on the coordination sphere as a fifth ligand, therefore the geometry is a pyramid with square base, but it is important to highlight an interesting feature. The crystallographic study shows a structure in which the bidentate ligands appears as the square base and the −NO 3 group as the apex, this structure seems to be rigid because the forces on the crystalline net compel the molecule to stay in that geometry; however, the calculations are made on free molecules, and they have enough degrees of freedom to search for another configuration and this phenomenon happens.…”

Section: Resultsmentioning

confidence: 77%

Indanone‐Based Copper(II) Molecular Materials as Potential Semiconductors for Optoelectronic Devices

et al. 2022

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A series of copper(II) molecular materials derived from 2‐benzylidene‐1‐indanones were synthesized in order to investigate the influence of their structure on their optical and semiconductor behavior. The molecular materials were structurally characterized by IR spectroscopy, mass spectrometry, and X‐ray diffraction. Additionally, thin films of copper complexes were successfully deposited by thermal evaporation, and the optical and electrical features of films were examined using UV‐vis spectroscopy and current‐voltage measurements, respectively. Subsequently, the structures of copper(II) complexes were optimized by density functional theory (DFT), and the energy values of the single occupied molecular orbital (SOMO) and lowest unoccupied molecular orbital (LUMO) were calculated. According the DFT calculations, the copper complexes show fluxional isomerism. Theoretical bandgap values were found to be consistent with those experimentally obtained and showed to be closely related with the p‐semiconductor behavior of copper complexes, which at the same time depends on the substituents in the structure.

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“…Casiopeinas and acetylacetonate analogues have been synthesized and studied by EPR and ENDOR spectroscopy. It has been found that small variations towards a square planar geometry can be detected by advanced EPR techniques [46,66].…”

Section: Activity and Propertiesmentioning

confidence: 99%

“…In the search for new, more effective, and less toxic drugs, Casiopeína ® (Cas) emerged [43]. A family of approximately 100 compounds has been synthesized from coordinated Cu(II) complexes with antineoplastic potential proven through cytotoxic action [44][45][46] (Figure 1).…”

Section: Introductionmentioning

confidence: 99%

The Importance of Being Casiopeina as Polypharmacologycal Profile (Mixed Chelate–Copper (II) Complexes and Their In Vitro and In Vivo Activities)

Aguilar-Jiménez,

Espinoza-Guillén,

Resendiz-Acevedo

et al. 2023

Inorganics

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In this review, we present a timeline that shows the origin of mixed chelate copper (II) complexes, registered as Mark Title Casiopeínas®, as the first copper (II) compounds proposed as anticancer drugs in 1988 and 1992. In the late twentieth century, the use of essential metals as anticancer agents was not even considered, except for their antifungal or antibacterial effects; also, copper, as gold salts, was used for arthritis problems. The use of essential metals as anticancer drugs to diminish the secondary toxic effects of Cisplatin was our driving force: to find less toxic and even more economical compounds under the rational design of metal chelate complexes. Due to their chemical properties, copper compounds were the choice to continue anticancer drug development. In this order of ideas, the rational designs of mixed chelate–copper (II) complexes (Casiopeínas, (Cas) homoleptic or heteroleptic, depending on the nature of the secondary ligand) were synthesized and fully characterized. In the search for new, more effective, and less toxic drugs, Casiopeína® (Cas) emerged as a family of approximately 100 compounds synthesized from coordinated Cu(II) complexes with proven antineoplastic potential through cytotoxic action. The Cas have the general formula [Cu(N–N)(N–O)]NO3 and [Cu(N–N)(O–O)]NO3, where N–N is an aromatic substituted diimine (1,10-phenanthroline or 2,2′-bipyridine), and the oxygen donor (O–O) is acetylacetonate or salicylaldehyde. Lately, some similar compounds have been developed by other research groups considering a similar hypothesis after Casiopeína’s discoveries had been published, as described herein. As an example of translational medicine criteria, we have covered each step of the established normative process for drug development, and consequently, one of the molecules (Casiopeína III ia (CasIIIia)) has reached the clinical phase I. For these copper compounds, other activities, such as antibacterial, antiparasitic and antiviral, have been discovered.

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Probing the structure of Copper(II)-Casiopeina type coordination complexes [Cu(O-O)(N-N)]+ by EPR and ENDOR spectroscopy

Cited by 7 publications

References 61 publications

Analysis of a Cu‐Doped Metal–Organic Framework, MFM‐520(Zn_1‐xCu_x), for NO₂ Adsorption

Analysis of a Cu‐Doped Metal–Organic Framework, MFM‐520(Zn_1‐xCu_x), for NO₂ Adsorption

Indanone‐Based Copper(II) Molecular Materials as Potential Semiconductors for Optoelectronic Devices

The Importance of Being Casiopeina as Polypharmacologycal Profile (Mixed Chelate–Copper (II) Complexes and Their In Vitro and In Vivo Activities)

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Probing the structure of Copper(II)-Casiopeina type coordination complexes [Cu(O-O)(N-N)]+ by EPR and ENDOR spectroscopy

Cited by 7 publications

References 61 publications

Analysis of a Cu‐Doped Metal–Organic Framework, MFM‐520(Zn1‐xCux), for NO2 Adsorption

Analysis of a Cu‐Doped Metal–Organic Framework, MFM‐520(Zn1‐xCux), for NO2 Adsorption

Indanone‐Based Copper(II) Molecular Materials as Potential Semiconductors for Optoelectronic Devices

The Importance of Being Casiopeina as Polypharmacologycal Profile (Mixed Chelate–Copper (II) Complexes and Their In Vitro and In Vivo Activities)

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Product

Resources

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Analysis of a Cu‐Doped Metal–Organic Framework, MFM‐520(Zn_1‐xCu_x), for NO₂ Adsorption

Analysis of a Cu‐Doped Metal–Organic Framework, MFM‐520(Zn_1‐xCu_x), for NO₂ Adsorption