Synthesis, Radiolabelling and Confocal Fluorescence Microscopy of Styrene‐Derivatised Bis(thiosemicarbazonato)zinc and ‐copper Complexes

Holland, Jason P.; Barnard, Peter J.; Bayly, Simon R.; Betts, Helen; Churchill, Grant C.; Dilworth, Jonathan R.; Edge, Ruth; Green, Jennifer C.; Hueting, Rebekka

doi:10.1002/ejic.200701351

Cited by 29 publications

(15 citation statements)

References 44 publications

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“…Previous studies have used a single global value of D 1/2 applied to each transition with nonzero f I values to generate the simulated spectra. 30,31 However, this arbitrary choice of D 1/2 prevents accurate comparison of the relative and absolute performance of each XC functional.…”

Section: Resultsmentioning

confidence: 99%

“…The syntheses and characterization of complexes 1-4 have been reported elsewhere. [29][30][31][32][33] the same level of theory. In each case, oscillator strengths and excitation energies for transition between the ground state and the first 24 excited stated states were calculated.…”

Section: Resultsmentioning

confidence: 99%

“…The syntheses and characterization of complex 1-4 have been reported elsewhere. 30,31,33 The optimized geometries have also been compared to three experimental X-ray crystal structures and the root-mean-squared deviation (RMSD/Å ) values are presented. 79,80 The results show that in almost all cases hybrid DFT functionals outperform pure functionals in both restricted and unrestricted TD-DFT calculations.…”

Section: Resultsmentioning

confidence: 99%

“…In each case, oscillator strengths and excitation energies for transition between the ground state and the first 24 excited stated states were calculated. In previous work, 30,31,33 we used the SWizard program 77 by Gorelsky to produce simulated UV/vis spectra based on the TD-DFT calculations. Each calculated transition between the ground and excited states I, can be modeled by, for example, a single Gaussian function in accordance with eq.…”

Section: Resultsmentioning

confidence: 99%

“…1). [29][30][31][32][33] These complexes are of particular interest in our continuing efforts towards developing copper complexes for in vivo positron emission tomography imaging of hypoxic tumors (tissue oxygenation levels pO 2 \3 mmHg).…”

Section: Introductionmentioning

confidence: 99%

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Evaluation of exchange‐correlation functionals for time‐dependent density functional theory calculations on metal complexes

Holland

Green

2009

J Comput Chem

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The electronic absorption spectra of a range of copper and zinc complexes have been simulated by using time-dependent density functional theory (TD-DFT) calculations implemented in Gaussian03. In total, 41 exchange-correlation (XC) functionals including first-, second-, and third-generation (meta-generalized gradient approximation) DFT methods were compared in their ability to predict the experimental electronic absorption spectra. Both pure and hybrid DFT methods were tested and differences between restricted and unrestricted calculations were also investigated by comparison of analogous neutral zinc(II) and copper(II) complexes. TD-DFT calculated spectra were optimized with respect to the experimental electronic absorption spectra by use of a Matlab script. Direct comparison of the performance of each XC functional was achieved both qualitatively and quantitatively by comparison of optimized half-band widths, root-mean-squared errors (RMSE), energy scaling factors (epsilon(SF)), and overall quality-of-fit (Q(F)) parameters. Hybrid DFT methods were found to outperform all pure DFT functionals with B1LYP, B97-2, B97-1, X3LYP, and B98 functionals providing the highest quantitative and qualitative accuracy in both restricted and unrestricted systems. Of the functionals tested, B1LYP gave the most accurate results with both average RMSE and overall Q(F) < 3.5% and epsilon(SF) values close to unity (>0.990) for the copper complexes. The XC functional performance in spin-restricted TD-DFT calculations on the zinc complexes was found to be slightly worse. PBE1PBE, mPW1PW91 and B1LYP gave the most accurate results with typical RMSE and Q(F) values between 5.3 and 7.3%, and epsilon(SF) around 0.930. These studies illustrate the power of modern TD-DFT calculations for exploring excited state transitions of metal complexes.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Evaluation of exchange‐correlation functionals for time‐dependent density functional theory calculations on metal complexes

Holland

Green

2009

J Comput Chem

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CoFe₂O₄@SiO₂@ Co (III) salen complex nanoparticle as a green and efficient magnetic nanocatalyst for the oxidation of benzyl alcohols by molecular O₂

Nasseri

Hemmat

Allahresani

et al. 2019

Applied Organom Chemis

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In the presence of cobalt (III) salen complex, selective oxidation of alcohols to carbonyl compounds was studied by molecular oxygen using isobutyraldehyde as an oxygen acceptor. The effect of cobalt (III) salen complex in the oxidation reaction was studied, and the results showed that Co (III) salen complex is very active and selective in the oxidation of various alcohols. Also, the effect of important factors including catalyst amount, solvent and temperature was investigated on the reaction. Furthermore, the catalytic activities of CoFe 2 O 4 @SiO 2 -supported Schiff base metal complex as well as the effect of molecular oxygen (O 2 ) as a green oxidant were studied. The results showed that benzaldehyde was the major product and the heterogeneous catalyst was highly reusable.

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Pyrene‐Functionalised Copper Complexes as Potential Dual‐Modality Imaging Agents

et al. 2009

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The syntheses of pyrene‐functionalised bis(thiosemicarbazonato)zinc and ‐copper complexes are reported. In contrast to previously reported bis(thiosemicarbazonato)Cu2+ complexes which are nonfluorescent, the pyrene group remains highly fluorescent. The compounds have been characterised by using a wide range of techniques including reverse‐phase HPLC, cyclic voltammetry, NMR, electronic absorption (UV/Vis), infrared and fluorescence emission spectroscopy. Spectroelectrochemistry experiments demonstrated that the Cu2+ complexes undergo quasi‐reversible one‐electron reduction at biologically accessible potentials. Density functional theory calculations were used to probe the electronic structure of the pyrene‐functionalised copper complexes and confirmed that the ligand‐based fluorescent emission occurs due to the absence of orbital interactions between the pyrene and bis(thiosemicarbazonato)copper groups. These preliminary studies demonstrate that the new copper complexes have potential to be used as dual‐modality agents for in vitro cellular fluorescence microscopy and in vivo positron emission tomography experiments.

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Synthesis, Radiolabelling and Confocal Fluorescence Microscopy of Styrene‐Derivatised Bis(thiosemicarbazonato)zinc and ‐copper Complexes

Cited by 29 publications

References 44 publications

Evaluation of exchange‐correlation functionals for time‐dependent density functional theory calculations on metal complexes

Evaluation of exchange‐correlation functionals for time‐dependent density functional theory calculations on metal complexes

CoFe₂O₄@SiO₂@ Co (III) salen complex nanoparticle as a green and efficient magnetic nanocatalyst for the oxidation of benzyl alcohols by molecular O₂

Pyrene‐Functionalised Copper Complexes as Potential Dual‐Modality Imaging Agents

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Synthesis, Radiolabelling and Confocal Fluorescence Microscopy of Styrene‐Derivatised Bis(thiosemicarbazonato)zinc and ‐copper Complexes

Cited by 29 publications

References 44 publications

Evaluation of exchange‐correlation functionals for time‐dependent density functional theory calculations on metal complexes

Evaluation of exchange‐correlation functionals for time‐dependent density functional theory calculations on metal complexes

CoFe2O4@SiO2@ Co (III) salen complex nanoparticle as a green and efficient magnetic nanocatalyst for the oxidation of benzyl alcohols by molecular O2

Pyrene‐Functionalised Copper Complexes as Potential Dual‐Modality Imaging Agents

Contact Info

Product

Resources

About

CoFe₂O₄@SiO₂@ Co (III) salen complex nanoparticle as a green and efficient magnetic nanocatalyst for the oxidation of benzyl alcohols by molecular O₂