New cyrhetrenyl and ferrocenyl sulfonamides: Synthesis, characterization, X-ray crystallography, theoretical study and anti- Mycobacterium tuberculosis activity

Quintana, Cristóbal; Silva, Gisella; Klahn, A. Hugo; Artigas, Vania; Fuentealba, Mauricio; Biot, Christophe; Halloum, Iman; Kremer, Laurent; Novoa, Néstor; Arancibia, Rodrigo

doi:10.1016/j.poly.2017.06.015

Cited by 43 publications

(13 citation statements)

References 60 publications

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“…This form is also the most stable isomer in the solid state, according to similar compounds previously reported (62,70,71). In addition, the cyrhetrenyl group adopts a typical three-legged piano-stool geometry, where the metal to centroid distance is 1.959(16) A, in good agreement with the other halfsandwich rhenium(I) compounds previously reported (72)(73)(74).…”

Section: Structural Descriptionsupporting

confidence: 87%

Spectroscopic Study of the E/Z Photoisomerization of a New Cyrhetrenyl Acylhydrazone: A Potential Photoswitch and Photosensitizer^†

Toro

Jara

Klahn

et al. 2020

Photochem & Photobiology

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The new cyrhetrenyl acylhydrazone [(CO)3Re(η5‐C5H4)‐C(O)‐NH‐N = C(CH3)‐(2‐C4H2S‐5‐NO2)] (E‐CyAH) has been designed, synthesized and fully characterized to study the effect of having a cyrhetrenyl fragment (sensitizer) covalently bonded to an acylhydrazone moiety (switch), on its photophysical and photochemical properties. The crystal structure reveals that E‐CyAH adopts an E‐configuration around the iminic moiety [‐N = C(CH3)]. The absorption spectrum of E‐CyAH displays two bands at 270 and 380 nm, which are mainly ascribed to π → π* intraligand (IL) and dπ → π* metal‐to‐ligand charge transfer (MLCT) transitions, being consistent with DFT/TD‐DFT calculations. Upon 365 nm irradiation, E‐CyAH photoisomerizes to Z‐CyAH, as evidenced by UV‐Vis and 1H‐NMR spectral changes, with a quantum yield value ΦE‐CyAH →Z‐CyAH of 0.30. Z‐CyAH undergoes a first‐order thermal back‐isomerization process, with a relatively short half‐life τ1/2 of 277 min. Consequently, E‐CyAH was quantitatively recovered after 24 h, making it a fully reversible T‐type molecular photoswitch. This remarkable behavior allows us to measure the individual photophysical properties for both isomers. In addition, E‐CyAH and Z‐CyAH efficiently photosensitize the generation of singlet oxygen (O2 (1Δg)) with good yield (ΦΔ = 0.342).

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Section: Structural Descriptionsupporting

confidence: 87%

Spectroscopic Study of the E/Z Photoisomerization of a New Cyrhetrenyl Acylhydrazone: A Potential Photoswitch and Photosensitizer^†

Toro

Jara

Klahn

et al. 2020

Photochem & Photobiology

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“…This phenomenon may be correlated with the electron-withdrawing property of the cyrhetrenyl moiety present in Bzn-1, compared to the electron-donating effect of the ferrocenyl fragment present in the analogue Bzn-2. Similar conclusions were previously reported by our group for hydrazones [79] and sulfonamides series [80] containing these organometallic moieties. Due to Fukui function, which is an important reactivity indicator in the framework DFT theory [60], we analyzed the condensed Fukui functions for Bzn-1 and Bzn-2 to explore which atoms are potential reactive sites for electrophilic, nucleophilic or radical attacks, respectively.…”

Section: Computational Calculationssupporting

confidence: 92%

ELECTROCHEMICAL, ESR, THEORETICAL STUDIES AND in vitro ANTI-T. cruzi ACTIVITY OF 2-ORGANOMETALLIC-5-NITRO-BENZIMIDAZOLES

Barriga-González¹,

Olivares-Petit²,

Toro³

et al. 2020

J. Chil. Chem. Soc.

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The bioorganometallic compounds 2-cyrhetrenyl-5-nitro-benzimidazole (Bzn-1) and 2-ferrocenyl-5-nitro-benzimidazole (Bzn-2) have been proposed as potential anti-Trypanosoma cruzi agents. In this regard, electrochemical, electron spin resonance and biological studies were carried out. Cyclic voltammetry experiments showed the generation of nitro anion radical derivatives and a self-protonation process was observed. Nitro anion radicals generated were characterized and analyzed using electron spin resonance spectroscopy. The compounds were tested in vitro against Trypanosoma cruzi (Dm28c strain). Biological evaluation display that 2cyrhetrenyl-5-nitro-benzimidazole (Bzn-1) was more active than its ferrocene analogue (Bzn-2) and purely organic derivate (Bzn-3), associated with the electronwithdrawing properties of the (η 5-C5H4)Re(CO)3 moiety. Finally, theoretical studies were carried out in order to elucidate the correlation between organometallic fragment, nitro-reduction potentials and trypanocidal activity.

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“…It is important to note that the chemical shifts of the NH resonance showed a clear dependence on the presence of the organometallic moiety bound to the iminic entity. In fact, the downfield shift observed for the cyrhetrenyl (1a-b) and cymantrenyl (2a-b) tosyl HYDs (Dd $ 0.30) compared with ferrocenyl analogues (3a-b) can be related to the electron-withdrawing properties of the (g 5 -C 5 H 4 )M(CO) 3 moieties 49 , which produce a deshielding of the NH resonance, thus, suggesting that the nature of the organometallic framework modifies the degree of electronic delocalisation on the -C(R) ¼ N-NH-unit. We have found similar results for ferrocenyl and cyrhetrenyl 1,3,4-thiadiazoles 50 and thiosemicarbazones 51 .…”

Section: Synthesis and Characterisation Of Bioorganometallichydrazones Derivatives From Sulphanilamidementioning

confidence: 99%

Bioorganometallic derivatives of 4-hydrazino-benzenesulphonamide as carbonic anhydrase inhibitors: synthesis, characterisation and biological evaluation

Brichet

Arancibia

Berrino

2020

Journal of Enzyme Inhibition and Medicinal Chemistry

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A series of bio-organometallic-hydrazones of the general formula [{(g 5 -C 5 H 4 )-C(R)¼N-N(H)-C 6 H 4 -4-SO 2 NH 2 }]MLn(MLn ¼ Re(CO) 3 , Mn(CO) 3 , FeCp; R¼H, CH 3 ) were prepared by reaction of formyl/acetyl organometallic precursors with 4-hydrazino-benzenesulphonamide. All compounds were characterized by conventional spectroscopic techniques (infra-red, 1 H and 13 C NMR, mass spectrometry and elemental analysis). Biological evaluation as carbonic anhydrase (CA, EC 4.2.1.1) inhibitors agents was carried out using four human/h) isoforms, hCA I, II, IX and XII. The cytosolic isoforms hCA I and II were effectively inhibited by almost all derivatives with inhibition constants of 1.7-22.4 nM. Similar effects were observed for the tumour-associated transmembrane isoform hCA XII (K I s of 1.9-24.4 nM). hCA IX was less sensitive to inhibition with these compounds. The presence of bio-organometallic or metallo-carbonyl moieties in the molecules of these CAIs makes them amenable for interesting pharmacologic applications, for example for compounds with CO donating properties.

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New cyrhetrenyl and ferrocenyl sulfonamides: Synthesis, characterization, X-ray crystallography, theoretical study and anti- Mycobacterium tuberculosis activity

Cited by 43 publications

References 60 publications

Spectroscopic Study of the E/Z Photoisomerization of a New Cyrhetrenyl Acylhydrazone: A Potential Photoswitch and Photosensitizer^†

Spectroscopic Study of the E/Z Photoisomerization of a New Cyrhetrenyl Acylhydrazone: A Potential Photoswitch and Photosensitizer^†

ELECTROCHEMICAL, ESR, THEORETICAL STUDIES AND in vitro ANTI-T. cruzi ACTIVITY OF 2-ORGANOMETALLIC-5-NITRO-BENZIMIDAZOLES

Bioorganometallic derivatives of 4-hydrazino-benzenesulphonamide as carbonic anhydrase inhibitors: synthesis, characterisation and biological evaluation

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New cyrhetrenyl and ferrocenyl sulfonamides: Synthesis, characterization, X-ray crystallography, theoretical study and anti- Mycobacterium tuberculosis activity

Cited by 43 publications

References 60 publications

Spectroscopic Study of the E/Z Photoisomerization of a New Cyrhetrenyl Acylhydrazone: A Potential Photoswitch and Photosensitizer†

Spectroscopic Study of the E/Z Photoisomerization of a New Cyrhetrenyl Acylhydrazone: A Potential Photoswitch and Photosensitizer†

ELECTROCHEMICAL, ESR, THEORETICAL STUDIES AND in vitro ANTI-T. cruzi ACTIVITY OF 2-ORGANOMETALLIC-5-NITRO-BENZIMIDAZOLES

Bioorganometallic derivatives of 4-hydrazino-benzenesulphonamide as carbonic anhydrase inhibitors: synthesis, characterisation and biological evaluation

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Spectroscopic Study of the E/Z Photoisomerization of a New Cyrhetrenyl Acylhydrazone: A Potential Photoswitch and Photosensitizer^†

Spectroscopic Study of the E/Z Photoisomerization of a New Cyrhetrenyl Acylhydrazone: A Potential Photoswitch and Photosensitizer^†