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Feiii, Cuii and Znii Complexes of the Rigid 9-Oxido-Phenalenone Ligand—Spectroscopy, Electrochemistry, and Cytotoxic Properties

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Feiii, Cuii and Znii Complexes of the Rigid 9-Oxido-Phenalenone Ligand—Spectroscopy, Electrochemistry, and Cytotoxic Properties International Journal of Molecular Sciences Article FeIII, CuII and ZnII Complexes of the Rigid 9-Oxido-phenalenone Ligand—Spectroscopy, Electrochemistry, and Cytotoxic Properties Katharina Butsch 1, Alexander Haseloer 1 , Simon Schmitz 1, Ingo Ott 2, Julia Schur 2 and Axel Klein 1,* 1 Department für Chemie, Institut für Anorganische Chemie, Universität zu Köln, Greinstraße 6, D-50939 Köln, Germany; [email protected] (K.B.); [email protected] (A.H.); [email protected] (S.S.) 2 Institute of Medicinal and Pharmaceutical Chemistry, Technische Universität Braunschweig, Beethovenstrasse 55, D-38106 Braunschweig, Germany; [email protected] (I.O.); [email protected] (J.S.) * Correspondence: [email protected] Abstract: The three complexes [Fe(opo)3], [Cu(opo)2], and [Zn(opo)2] containing the non-innocent anionic ligand opo− (opo− = 9-oxido-phenalenone, Hopo = 9-hydroxyphenalonone) were synthe- 1 sised from the corresponding acetylacetonates. [Zn(opo)2] was characterised using H nuclear magnetic resonance (NMR) spectroscopy, the paramagnetic [Fe(opo)3] and [Cu(opo)2] by electron paramagnetic resonance (EPR) spectroscopy. While the EPR spectra of [Cu(opo)2] and [Cu(acac)2] in dimethylformamide (DMF) solution are very similar, a rather narrow spectrum was observed for [Fe(opo)3] in tetrahydrofuran (THF) solution in contrast to the very broad spectrum of [Fe(acac)3] in − Citation: Butsch, K.; Haseloer, A.; THF (Hacac = acetylacetone, 2,4-pentanedione; acac = acetylacetonate). The narrow, completely Schmitz, S.; Ott, I.; Schur, J.; Klein, A. isotropic signal of [Fe(opo)3] disagrees with a metal-centred S = 5/2 spin system that is observed FeIII, CuII and ZnII Complexes of the in the solid state. We assume spin-delocalisation to the opo ligand in the sense of an opo− to FeIII Rigid 9-Oxido-phenalenone electron transfer. All compounds show several electrochemical opo-centred reduction waves in the Ligand—Spectroscopy, range of −1 to −3 V vs. the ferrocene/ferrocenium couple. However, for CuII and FeIII the very Electrochemistry, and Cytotoxic first one-electron reductions are metal-centred. Electronic absorption in the UV to vis range are Properties. Int. J. Mol. Sci. 2021, 22, due to π–π* transitions in the opo core, giving Hopo and [Zn(opo)2] a yellow to orange colour. The 3976. https://doi.org/10.3390/ structured bands ranging from 400 to 500 for all compounds are assigned to the lowest energy π−π* ijms22083976 transitions. They show markedly higher intensities and slight shifts for the CuII (brown) and FeIII II III Academic Editor: Antonello Merlino (red) complexes and we assume admixing metal contributions (MLCT for Cu , LMCT for Fe ). For both complexes long-wavelength absorptions assignable to d–d transitions were detected. Detailed Received: 30 March 2021 spectroelectrochemical experiments confirm both the electrochemical and the optical assignments. Accepted: 7 April 2021 Hopo and the complexes [Cu(opo)2], [Zn(opo)2], and [Fe(opo)3] show antiproliferative activities Published: 12 April 2021 against HT-29 (colon cancer) and MCF-7 (breast cancer) cell lines in the range of a few µM, comparable to cisplatin under the same conditions. Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in Keywords: Iron; copper; zinc; 9-oxido-phenalenone; antiproliferative; redox published maps and institutional affil- iations. 1. Introduction Although 9-hydroxyphenalenone (Hopo) was first synthesised 80 years ago [1], till Copyright: © 2021 by the authors. about 10 years ago the coordination chemistry of the anionic 9-oxido-phenalenone (opo−) Licensee MDPI, Basel, Switzerland. ligand (Scheme1, left) was rather underdeveloped. Most of the reports were on the proton This article is an open access article tautomerism [2–9] and tunnelling effects [10] of the Hopo molecule which are far more distributed under the terms and pronounced than for the corresponding parent acetyl acetone system. When coordinating conditions of the Creative Commons deprotonated opo− to metals, stable six-ring chelates stabilise the complexes and two one- Attribution (CC BY) license (https:// electron ligand-centred reductions (opo−/opo2− and opo2−/opo3−) and one one-electron creativecommons.org/licenses/by/ oxidation of the ligand (opo−/opo) should be accessible (Scheme1, right). The 13 e − 4.0/). Int. J. Mol. Sci. 2021, 22, 3976. https://doi.org/10.3390/ijms22083976 https://www.mdpi.com/journal/ijms Int. J. Mol. Sci. 2021, 22, x FOR PEER REVIEW 2 of 18 Int. J. Mol. Sci. 2021, 22, 3976 2 of 18 electron ligand-centred reductions (opo−/opo2− and opo2−/opo3−) and one one-electron oxi- dation of the ligand (opo−/opo) should be accessible (Scheme 1, right). The 13 e‒ opo• and opo• and the 15 e− opo•2− are radical species. Not surprisingly, opo complexes of the the 15 e‒ opo•2− are radical species. Not surprisingly, opo complexes of the main group main group elements Be, B have been investigated till today towards their conducting elements Be, B have been investigated till today towards their conducting abilities [11– abilities [11–16]. 16]. (a) (b) (c) SchemeScheme 1. 1.( a(a)) 9-Hydroxyphenalenone 9-Hydroxyphenalenone (Hopo), (Hopo), a a derivative derivative of of acetylacetone acetylacetone (Hacac). (Hacac). Both Both are are able able to to form form six-ring six-ring chelates chelates when deprotonated. Structure of the cytotoxic Hypocrellin A. (b) Selected resonance structures of the anionic 14 valence when deprotonated. Structure of the cytotoxic Hypocrellin A. (b) Selected resonance structures of the anionic 14 valence electron electron system 9-oxido-phenaleneone (opo‒) with reduced and oxidised forms. (c) The o-quinone–semiquinone–cate- system 9-oxido-phenaleneone (opo−) with reduced and oxidised forms. (c) The o-quinone–semiquinone–catecholate triad. cholate triad. In contrast to the simplest β-diketonate ligand acetylacetonate (acac−) (Scheme1), In contrast to the simplest β-diketonate ligand acetylacetonate (acac−) (Scheme 1), which has been used extensively to coordinate main group and transition metals [17–20], opowhich complexes has been are used expected extensively to be to quite coordinate similar tomain the group corresponding and transition acac complexes, metals [17–20], but wereopo complexes rather scarce are till expected about 2010. to be Early quite reports similar on to opothe corresponding complexes of Mn acacII, Fecomplexes,III, CoII, Ni butII, wereII ratherII scarce till2+ about 2010. Early reports on opo complexes of MnII, FeIII, CoII, NiII, Cu , Zn , and UO2 do not contain detailed characterisations or applications [21–23]. II II 2+ ACu number, Zn , and of main-group UO2 do not metal contain complexes detailed containing characterisations BIII [11 –or16 applications], SiIV [24], Ge[21–23].IV [24 ],A III IV IV II BenumberII [11,21 of], main-group or AlIII [21, 25metal] or complexes the f-elements containing NdIII [ 25B ,26 [11–16],], EuIII Si[25 –[24],27], DyGeIII [24],[25, 28Be], III III III III III Er[11,21],III [25, 26or], Al and [21,25] YbIII [ 25or, 26the] weref-elements studied Nd till 2010,[25,26], the Eu latter [25–27], with interesting Dy [25,28], luminescence Er [25,26], properties.and YbIII [25,26] were studied till 2010, the latter with interesting luminescence properties. InIn aa benchmarking benchmarking study study of of the the opo opo complexes complexes of of Rh RhI,I Pd, PdIIIIand and Pt PtIIII,, their their cytotoxic cytotoxic activitiesactivities againstagainst HL60HL60 humanhuman acute acute myeloid myeloid leukemia leukemia cell cell lines lines were were reported reported in in 2006 2006 to to II II 3 2++ bebe comparablecomparable toto that that of of cisplatin cisplatin [ 29[29].]. After After that, that, the the opo opo Pt Ptcomplex complex [Pt(opo)(NH [Pt(opo)(NH3)2)] ] waswas studied studied through through DFT DFT calculations calculations alongside alongside other other PtII-containing PtII-containing complexes complexes with anti-with canceranti-cancer activities activities [30], and [30], very and recently very recently [Pt(opo)(dach)](NO [Pt(opo)(dach)](NO3) (dach3 =) (dach 1,2-diaminocyclohexane) = 1,2-diaminocy- wasclohexane) found to was have found high antiproliferativeto have high antiproliferative activity in a murine activity NSCLC in a murine (lung cancer) NSCLC tumour (lung modelcancer) [ 31tumour]. This model is not [31]. surprising This is since not surpri derivativessing since of Hopo derivatives [32,33 ]of and Hopo especially [32,33] theand naturallyespecially occurring the naturally derivatives occurring Hypocrellin derivatives A Hypocrellin and B (Scheme A and1) haveB (Scheme been studied1) have been for quitestudied some for timequite for some their time cytotoxic for their properties cytotoxic [properties34–36]. Furthermore, [34–36]. Furthermore, Hypocrellin Hypocrel- deriva- tiveslin derivatives [37,38] and [37,38] complexes and complexes of ZnII [39 of], Zn CuIIII [39],[40], Cu CoIIIII [40],[41 ],Co AuIII [41],III, and Au PtIII, IVand[42 Pt]IV were [42] investigatedwere investigated for their for photonuclease their photonuclease activity. activity. Moreover, Moreover, a Hypocrellin a Hypocrellin A ZnII complex A ZnII com- was reportedplex was for reported the optical for the recognition optical recognition of pyrophosphate of pyrophosphate [43]. [43]. SinceSince about about 2010, 2010, researchers researchers have have recognised recognised the the enormous enormous potential potential of of the the so-called so-called non-innocentnon-innocent ligand ligand opo opo− −with with its its high high similarity similarity to to the theo-semiquinones o-semiquinones (Scheme (Scheme1) [ 18 1), 44[18,44––48]. In complexes of non-innocent ligands, the ligands can have variable charges and oxidation Int. J. Mol. Sci. 2021, 22, 3976 3 of 18 states, thus making the metal oxidation state ambiguous [18]. Opo complexes of main-group and transition metals are therefore intensely studied for their magnetic, electron- and charge- transfer phenomena [44–55] as well as for their use in electroactive materials [51–59] or in electron transfer or related catalysis [53,55,57,60–70].
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