Induction of E/Z isomerization in a pendant metal-bound azobenzene: a synthetic, spectroscopic and theoretical study

Hasheminasab, Abed; Wang, L.; Dawadi, Mahesh B.; Bass, Jacob; Herrick, Richard S.; Rack, Jeffrey J.; Ziegler, Christopher J.

doi:10.1039/c5dt02480c

Cited by 20 publications

(11 citation statements)

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“…A previously reported approach for the combinatorial synthesis of anticancer ruthenium-arene complexes exploited the metal-templated condensation of anilines with picolinaldehydes to yield new compounds bearing pyridylimine ligands. , Based on the promising anticancer activities of rhenium(I) tricarbonyl complexes, we aimed to adapt this condensation chemistry for the generation of a diverse library of these compounds. The feasibility of this strategy was bolstered by previous studies that have demonstrated that Re(CO) 5 Cl acts as an appropriate template for aniline-picolinaldehyde condensation chemistry to afford rhenium(I) tricarbonyl complexes bearing pyridylimine ligands. − …”

Section: Resultsmentioning

confidence: 99%

“…All reagents were purchased from commercial vendors. The lead rhenium complexes and the corresponding free ligands were synthesized according to literature methods with slight modifications. , All reactions were performed under ambient atmospheric conditions without any efforts to exclude oxygen or water. Solvents used were of ACS grade or higher.…”

Section: Methodsmentioning

confidence: 99%

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Combinatorial Synthesis to Identify a Potent, Necrosis-Inducing Rhenium Anticancer Agent

et al. 2019

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Combinatorial synthesis can be applied for developing a library of compounds that can be rapidly screened for biological activity. Here, we report the application of microwave-assisted combinatorial chemistry for the synthesis of 80 rhenium(I) tricarbonyl complexes bearing diimine ligands. This library was evaluated for anticancer activity in three different cancer cell lines, enabling the identification of three lead compounds with cancer cell growth-inhibitory activities of less than 10 μM. These three lead structures, Re-9B, Re-9C, and Re-9D, were synthesized independently and fully characterized by NMR spectroscopy, mass spectrometry, elemental analysis, and X-ray crystallography. The most potent of these three complexes, Re-9D, was further explored to understand its mechanism of action. Complex Re-9D is equally effective in both wild-type and cisplatin-resistant A2780 ovarian cancer cells, indicating that it circumvents cisplatin resistance. This compound was also shown to possess promising activity against ovarian cancer tumor spheroids. Additionally, flow cytometry showed that Re-9D does not induce cell cycle arrest or flipping of phosphatidylserine to the outer cell membrane. Analysis of the morphological changes of cancer cells treated with Re-9D revealed that this compound gives rise to rapid plasma membrane rupture. Collectively, these data suggest that Re-9D induces necrosis in cancer cells. To assess the in vivo biodistribution and stability of this compound, a radioactive 99mTc analogue of Re-9D, 99mTc-9D(H2O), was synthesized and administered to naı̈ve BALB/c mice. Results of these studies indicate that 99mTc-9D(H2O) exhibits high metabolic stability and a distinct biodistribution profile. This research demonstrates that combinatorial synthesis is an effective approach for the development of new rhenium anticancer agents with advantageous biological properties.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Combinatorial Synthesis to Identify a Potent, Necrosis-Inducing Rhenium Anticancer Agent

et al. 2019

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“…Re(CO) 3 diimine complexes exhibit metal-to-ligand charge-transfer (MLCT) transitions that show much higher molar absorbtivity (>5 times higher for 4 and 5 , and ~20 times higher for 6 and 7 ). The molar absorptivities of 4 and 5 were comparable to those observed in mono-rhenium tricarbonyl Schiffs base compounds with absorptivities around 3,000–4,000 M −1 cm −1 [44,45]. Complexes ( 6 and 7 ) show stronger absorbtivities in the range of 7,000–8,000 M −1 cm −1 , about twice as much as those of monomeric Re(CO) 3 Schiff’s base complexes, which is consistent with their dimeric structures [41,46].…”

Section: 0 Results and Discussionmentioning

confidence: 74%

“…Thus, we can readily generate a connection to a Re(CO) 3 center using metal-mediated Schiff base formation, as shown in Figure 1. We and others have used this reaction to append a wide variety of molecules to the Re(CO) 3 , including aryl rings, fluorescent compounds, peptides and isomerizable groups like azobenzene [44]. These reactions can be carried out using one-pot conditions, and thus for the synthesis of conjugate systems is an attractive way to obtain a variety of structures.…”

Section: 0 Results and Discussionmentioning

confidence: 99%

Using hydrazine to link ferrocene with Re(CO)3: A modular approach

Chanawanno

Rhoda

Hasheminasab

et al. 2016

Journal of Organometallic Chemistry

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Acetyl ferrocene and diacetyl ferrocene both readily react with an excess of hydrazine to afford the corresponding hydrazone compounds. These compounds can then be linked to Re(CO)3 via a metal-mediated Schiff base reaction, resulting in a series of ferrocene-Re(CO)3 conjugates with different stoichiometries. Conjugates with 1:1, 1:2, and 2:1 ferrocene: Re(CO)3 ratios can be produced via this “modular” type synthesis approach. Several examples of these conjugates were structurally characterized, and their spectroscopic, electrochemical, and spectroelectrochemical behaviors were investigated. The electronic structures of these compounds were also probed using DFT and TDDFT calculations.

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“…1–6 This interest arises from both its notable properties as a non-labile unit with a rigid facial geometry as well as its use as a synthon for a wide variety of functional inorganic complexes. 7–10 Recently, we have used the Re(CO) 3 moiety as a template to produce isoindoline based chelates that can be considered as half of a phthalocyanine or a hemiporphyrazine (a “semihemiporphyrazine”). 11,12 The limited geometry options and inert nature of this metal unit in both cases prevent larger macrocycles or chelates from forming.…”

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confidence: 99%

Re(CO)₃-Templated Synthesis of α-Amidinoazadi(benzopyrro)methenes

et al. 2017

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α-amidino azadi(benzopyrro)methenes were synthesized using the Re(CO)3 unit as a templating agent. The products of these template reactions are six-coordinate Re complexes, with a facial arrangement of carbonyls, a non-coordinating anion, and a tridentate α-amidino azadi(benzopyrro)methene ligand. The tridentate ligand shows the conversion of one diiminoisoindoline sp2 carbon to a sp3 carbon which has been seen in the “helmet” and bicyclic phthalocyanines. The bidentate diiminoisoindoline fragment tilts out of the plane of coordination. Five examples of α-amidino azadi(benzopyrro)methenes were produced from these reactions using different nitrile solvents, including the nitrile activation of acetonitrile, propionitrile, butyronitrile, cyclohexanecarbonitrile, and benzonitrile were formed.

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Induction of E/Z isomerization in a pendant metal-bound azobenzene: a synthetic, spectroscopic and theoretical study

Cited by 20 publications

References 40 publications

Combinatorial Synthesis to Identify a Potent, Necrosis-Inducing Rhenium Anticancer Agent

Combinatorial Synthesis to Identify a Potent, Necrosis-Inducing Rhenium Anticancer Agent

Using hydrazine to link ferrocene with Re(CO)3: A modular approach

Re(CO)₃-Templated Synthesis of α-Amidinoazadi(benzopyrro)methenes

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Induction of E/Z isomerization in a pendant metal-bound azobenzene: a synthetic, spectroscopic and theoretical study

Cited by 20 publications

References 40 publications

Combinatorial Synthesis to Identify a Potent, Necrosis-Inducing Rhenium Anticancer Agent

Combinatorial Synthesis to Identify a Potent, Necrosis-Inducing Rhenium Anticancer Agent

Using hydrazine to link ferrocene with Re(CO)3: A modular approach

Re(CO)3-Templated Synthesis of α-Amidinoazadi(benzopyrro)methenes

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Re(CO)₃-Templated Synthesis of α-Amidinoazadi(benzopyrro)methenes