Comment on "Disclosing Cyclic(Alkyl)(Amino)Carbenes as a One-Electron Reductant: Synthesis of Acyclic(Amino)(Aryl)Carbene-Based Kekulé Diradicaloids".

This correspondence addresses a misassignment of an EPR spectrum of 2 in a recent publication (Chem. Eur. J. 2022, 28, e202104567) by Dr. Jana and co-workers. The original authors have prepared this correspondence together with Dr. Korth.

Disclosing Cyclic(Alkyl)(Amino)Carbenes as One-Electron Reductants: Synthesis of Acyclic(Amino)(Aryl)Carbene-Based Kekulé Diradicaloids.

Herein, we disclose cyclic(alkyl)(amino)carbenes (CAACs) to be one-electron reductants under the formation of a transient radical cation as indicated by EPR spectroscopy. The disclosed CAAC reducing reactivity was used to synthesize acyclic(amino)(aryl)carbene-based Thiele and Chichibabin hydrocarbons, a new class of Kekulé diradicaloids. The results demonstrate CAACs to be potent organic reductants. Notably, the acyclic(amino)(aryl)carbene-based Chichibabin's hydrocarbon shows an appreciable population of the triplet state at room temperature, as evidenced by both variable-temperature NMR and EPR spectroscopy.

Crystallographic Elucidation of Stimuli-Controlled Molecular Rotation for a Reversible Sol-Gel Transformation.

To get an idea about the most probable microporous supramolecular environment in the gel state, gelator molecule 1 has been crystallized from its gelling solvent (dimethylformamide). Crystal structure analysis of 1 shows a strong π···π stacking interaction between the electron-deficient pentafluorophenyl ring and electron-rich naphthyl ring. The gelling solvent situated in the "molecular pocket" stitches the gelators through weak H-bonding interactions to facilitate the formation of an organogel. Scanning electron microscopy analysis exhibits a ribbonlike fibrous morphology that resembles the supramolecular arrangement of 1 in its crystalline state, as evidenced by powder X-ray diffraction. In the presence of external stimuli (tetrabutylammonium fluoride), the organogel of 1 disassembles into sol. This sol-gel transformation phenomenon has been explained on the basis of X-ray single-crystal analysis. Single crystals obtained from the sol state show that naphthylic -OH of 1 gets deprotonated, resulting in C-C bond rotation that plays a major role in the sol-gel transformation. Gelator 1 exhibits weak green fluorescence in the gel state, whereas it shows highly intense yellow fluorescence in the sol state. Furthermore, a reversible sol-gel transformation associated with changes in the spectroscopic properties has been observed in the presence of acids and fluoride ions, respectively.

Redox Cascades and Making of a C-C Bond: 1,2-Benzodiazinyl Radicals and a Copper Complex of a Benzodiazine.

Two 1,2-benzodiazinyl radicals, cinnolinyl radicals by name, were successfully isolated by cascade routes using 1,4-naphthoquinone as a precursor. Reaction of 1,4-naphthoquinone with hydrazine hydrate promotes a (5e + 5H+) redox cascade affording benzo[ g]naphtho[1,2- c]cinnolinyl-7,12,14-trione (Cn•) in 69% yields, while the similar reaction with 2-hydrazinopyridine is a (7e + 7H+) oxidative cascade and furnishes N-pyridinecinnolinyl radical (PyCn•). The cascades are composed of C-N and C-C bond making reactions. The neutral even alternate arenes are always diamagnetic; thus, the isolation of Cn• and PyCn• is a breakthrough. The Cn•/Cn- and PyCn•/PyCn- redox couples are reversible, and the reaction of Cn• with [CuI(PPh3)3Cl] in the presence of hydrazine hydrate and Et3N affords a Cn- complex of copper(I), [(Cn-)CuI(PPh3)2] (1). Similar to phenalenyl radical, PyCn• exists in three redox states, PyCn+, PyCn•, and PyCn-, in a smaller potential range (-0.30 V to -0.60 V vs Fc+/Fc couple) and can be used as an oxidant as well as a reductant. PyCn• acts as a catalyst for the oxidative cleavages of benzil to benzoic and 2,2'-pyridil to picolinic acids in methanol in the presence of air. The molecular and electronic structures of Cn•, PyCn•, and 1·1/2MeOH were confirmed by single crystal X-ray crystallography, EPR spectroscopy, and DFT calculations.

Orthometalated N-(Benzophenoxazine)-o-aminophenol: Phenolato versus Phenoxyl States.

The molecular and electronic structures of the orthometalated ruthenium(III) and osmium(III) complexes of N-(benzophenoxazine)-o-aminophenol (OXLH2) that exhibits versatile redox activities are reported. The redox chemistry of OXLH2 is remarkably different from that of N-(aryl)-o-aminophenol (APLH2). The study established that OXLH2 is redox noninnocent and is a precursor of a phenoxyl radical. One of the C-H bonds of OXLH2 is activated by ions, and OXLH2 reveals three different redox states as dianionic phenolato (OXL2-), monoanionic phenoxyl radical (OXL•-), and zwitterionic phenoxium cation (OXL±) states. The reaction of OXLH2 with [RuII(PPh3)3Cl2] in boiling toluene in air affords an orthometalated OXL2- complex of ruthenium(III), trans-[(OXL2-)RuIII(PPh3)2(Cl)] (1), whereas the similar reaction with [OsII(PPh3)3Br2] yields an orthometalated OXL•- complex, cis-[(OXL•-)OsIII(PPh3)Br2] (2). 1 and 2 exhibit ligand-based reversible redox waves due to OXL•-/OXL2-, OXL±/OXL•-, and MIII/MII couples. The 1 + ion is a OXL•- complex of ruthenium(III). 2 - exhibits temperature-dependent valence tautomerism due to [OsII(OXL•-) ↔ OsIII(OXL2-)] equilibrium. 2 2- is a OXL2- complex of osmium(II), while 1 2+ and 2 + are OXL± complexes of metal(III). 2 is an oxidant and effective catalyst for oxidation of 3,5-di-tert-butylcatechol to the corresponding quinone, and the turnover number is 119.7 h-1. The UV-vis-NIR absorption spectrum of 1 displays an NIR band at 800 nm due to an intra-ligand-charge-transfer transition, which is absent in 2 incorporating a OXL•- radical. The molecular and electronic structures of 1 and 2 and their oxidized and reduced analogues were confirmed by single-crystal X-ray crystallography, variable-temperature electron paramagnetic resonance spectroscopy, spectroelectrochemical measurements, and density functional theory calculations.

Exploring the effect of substituent in the hydrazone ligand of a family of µ-oxidodivanadium(v) hydrazone complexes on structure, DNA binding and anticancer activity.

The reaction of 2-hydroxybenzoylhydrazine (H2bh) separately with equimolar amounts of [VIVO(aa)2] and [VIVO(ba)2] in CHCl3 afforded the complexes [VO3(HL1)2] (1) and [VO3(HL2)2] (2) respectively in good to excellent yield ((HL1)2- and (HL2)2- represent respectively the dianionic form of 2-hydroxybenzoylhydrazones of acetylacetone (H3L1) and benzoylacetone (H3L2) (general abbreviation H3L)). From X-ray structure analysis, the VV-O-VV angle was found to be ∼115° and 180° in 1 and 2 respectively. Upon one-electron reduction selectively at one V centre at an appropriate potential, each of 1 and 2 generated mixed-valence [(HL)VVO-(µ-O)-OVIV(HL)]- species 1A and 2A respectively, which showed valence delocalization at room temperature and localization at 77 K, and the VIV-O-VV bond angles were calculated to be 177.5° and 180° respectively. The intercalative mode of binding of the two complexes 1 and 2 with CT DNA has been suggested by UV-visible spectroscopy (Kb = 7.31 × 105 M-1 and 8.71 × 105 M-1 respectively for 1 and 2), fluorescence spectroscopy (Ksv = 6.85 × 105 M-1 and 8.53 × 105 M-1 respectively for 1 and 2) and circular dichroism spectroscopy. Such intercalative mode of binding of these two complexes with CT DNA and HPV DNA has also been confirmed by molecular docking study. Both complexes 1 and 2 exhibited promising anti-cancer activity against SiHa cervical cancer cells with IC50 values of 28 ± 0.5 µM and 25 ± 0.5 µM respectively for 24 h which is significantly better than that of widely used cisplatin (with IC50 value of 63.5 µM). Nuclear staining experiments reveal that these complexes kill the SiHa cells through apoptotic mode. It is interesting to note that these two complexes are non-toxic to normal T293 cell line. Complex 2 showed higher DNA binding ability with CT DNA and HPV DNA as well as better anti-cancer properties towards SiHa cervical cancer cells in comparison to complex 1, a fact which can be explained by considering the lower energy of LUMO (which favours electron transition from DNA to the metal complex) and also the higher surface area of complex 2 in comparison to complex 1 due to the presence of one extra electron-withdrawing phenyl group in the former.

Cobalt Ion Promoted Redox Cascade: A Route to Spiro Oxazine-Oxazepine Derivatives and a Dinuclear Cobalt(III) Complex of an N-(1,4-Naphthoquinone)-o-aminophenol Derivative.

The study discloses that the redox activity of N-(1,4-naphthoquinone)-o-aminophenol derivatives (LRH2) containing a (phenol)-NH-(1,4-naphthoquinone) fragment is notably different from that of a (phenol)-NH-(phenol) precursor. The former is a platform for a redox cascade. LRH2 is redox noninnocent and exists in Cat-N-(1,4-naphthoquinone)(2-) (LR 2-) and SQ-N-(1,4-naphthoquinone) (LR •-) states in the complexes. Reactions of LRH2 with cobalt(II) salts in MeOH in air promote a cascade affording spiro oxazine-oxazepine derivatives (OXLR) in good yields, when R = H, Me, tBu. Spiro oxazine-oxazepine derivatives are bioactive, and such a molecule has so far not been isolated by a schematic route. In this context this cascade is significant. Dimerization of LRH2 → OXLR in MeOH is a (6H+ + 6e) oxidation reaction and is composed of formations of four covalent bonds and 6-exo-trig and 7-endo-trig cyclization based on C-O coupling reactions, where MeOH is the source of a proton and the ester function. It was established that the active cascade precursor is [(LMe •-)CoIIICl2] (A). Notably, formation of a spiro derivative was not detected in CH3CN and the reaction ends up furnishing A. The route of the reaction is tunable by R, when R = NO2, it is a (2e + 4H+) oxidation reaction affording a dinuclear LR 2- complex of cobalt(III) of the type [(LNO2 2-)2CoIII2(OMe)2(H2O)2] (1) in good yields. No cascade occurs with zinc(II) ion even in MeOH and produces a LMe •- complex of type [(LMe •-)ZnIICl2] (2). The intermediate A and 2 exhibit strong EPR signals at g = 2.008 and 1.999, confrming the existence of LMe •- coordinated to low-spin cobalt(III) and zinc(II) ions. The intermediates of LRH2 → OXLR conversion were analyzed by ESI mass spectrometry. The molecular geometries of OXLR and 1 were confirmed by X-ray crystallography, and the spectral features were elucidated by TD DFT calculations.

Exploring the effect of hydroxylic and non-hydroxylic solvents on the reaction of [VIVO(ß-diketonate)2] with 2-aminobenzoylhydrazide in aerobic and anaerobic conditions.

Refluxing [VIVO(ß-diketonate)2], namely [VIVO(acetylacetonate)2] and [VIVO(benzoylacetonate)2], separately with an equivalent or excess amount of 2-aminobenzoylhydrazide (ah) in laboratory grade (LG) CH3OH in aerobic conditions afforded non-oxidovanadium(iv) and oxidovanadium(v) complexes of the type [VIV(L1)2] (1), [VVO(L1)(OCH3)]2 (3) and [VIV(L2)2] (2), and [VVO(L2)(OCH3)] (4), respectively. (L1)2- and (L2)2- represent the dianionic forms of 2-aminobenzoylhydrazone of acetylacetone (H2L1) and benzoylacetone (H2L2), respectively, (general abbreviation, H2L), which was formed by the in situ condensation of ah with the respective coordinated [ß-diketonate] in medium-to-good yield. The yield of different resulting products was dependent upon the ratio of ah to [VIVO(ß-diketonate)2]. For example, the yield of 1 and 2 complexes increased significantly associated with a decrease in the amount of 3 and 4 with an increase in the molar ratio of ah. Upon replacing CH3OH by a non-hydroxylic solvent, LG CHCl3, the above reaction yielded only oxidovanadium(v) complexes of the type [VVO(L1)(OH)]2 (5), [VVO(L2)(OH)] (6) and [VO3(L)2] (7, 8) whereas, upon replacing CHCl3 by another non-hydroxylic solvent, namely LG CH3CN, only the respective [VO3(L)2] (7, 8) complex was isolated in 72-78% yield. However, upon performing the above reactions in the absence of air using dry CH3OH or dry CHCl3, only the respective [VIV(L)2] complex was obtained, suggesting that aerial oxygen was the oxidising agent and the type of pentavalent product formed was dependent upon the nature of solvent used. Complexes 3 and 4 were converted, respectively, to 7 and 8 on refluxing in LG CHCl3via the respective unstable complex 5 and 6. The DFT calculated change in internal energy (ΔE) for the reactions 2[VVO(L2)(OCH3)] + 2H2O → 2[VVO(L2)(OH)] + 2CH3OH and 2[VVO(L2)(OH)] → [VO3(L2)2] + H2O was, respectively, +3.61 and -7.42 kcal mol-1, suggesting that the [VVO(L2)(OH)] species was unstable and readily transformed to the stable [VO3(L2)2] complex. Upon one-electron reduction at an appropriate potential, each of 7 and 8 generated mixed-valence [(L)VVO-(µ-O)-OVIV(L)]- species, which showed valence-delocalisation at room temperature and localisation at 77 K. Some of the complexes showed a wide range of toxicity in a dose-dependent manner against lung cancer cells comparable with that observed with cis-platin.

Molecular and Electronic Structures of Ruthenium Complexes Containing an ONS-Coordinated Open-Shell π Radical and an Oxidative Aromatic Ring Cleavage Reaction.

The coordination chemistry of 2,4-di-tert-butyl-6-[(2-mercaptophenyl)amino]phenol (LONSH3), which was isolated as a diaryl disulfide form, (LONSH2)2, with a Ru ion is disclosed. It was established that the trianionic LONS3- is redox-noninnocent and undergoes oxidation to either a closed-shell singlet (CSS), LONS-, or an open-shell π-radical state, LONS•2-, and the reactivities of the [RuII(LONS•2-)] and [RuII(LONS-)] states are different. The reaction of (LONSH2)2 with [Ru(PPh3)3Cl2] in toluene in the presence of PPh3 affords a ruthenium complex of the type trans-[Ru(LONS)(PPh3)2Cl] (1), while the similar reaction with [Ru(PPh3)3(H)(CO)Cl] yields a LONS•2- complex of ruthenium(II) of the type trans-[RuII(LONS•2-)(PPh3)2(CO)] (2). 1 is a resonance hybrid of the [RuII(LONS-)Cl] and [RuIII(LONS•2-)Cl] states. It is established that 2 incorporating an open-shell π-radical state, [RuII(LONS•2-)(CO)], reacts with an in situ generated superoxide ion and promotes an oxidative aromatic ring cleavage reaction, yielding a α-N-arylimino-ω-ketocarboxylate (LNS2-) complex of the type [RuII(LNS2-)(PPh3)(CO)]2 (4), while 1 having a CSS state, [RuII(LONS-)Cl], is inert in similar conditions. Notably, 2 does not react with O2 molecule but reacts with KO2 in the presence of excess PPh3, affording 4. The redox reaction of (LONSH2)2 with [Ru(PPh3)3Cl2] in ethanol in air is different, leading to the oxidation of LONS to a quinone sulfoxide derivative (LONSO0) as in cis-[RuII(LONSO0)(PPh3)Cl2] (3), via 1 as an intermediate. The molecular and electronic structures of 1-4 were established by single-crystal X-ray crystallography, electron paramagnetic resonance spectroscopy, electrochemical measurements, and density functional theory calculations. 1+ is a resonance hybrid of [RuIII(LONS-)(PPh3)2Cl ↔ RuIV(LONS•2-)(PPh3)2Cl]+ states, 2- is a LONS3- complex of ruthenium(II), [RuII(LONS3-)(PPh3)2(CO)]-, and 2+ is a ruthenium(II) complex of LONS- of the type [RuII(LONS-)(PPh3)2(CO)]+, where 35% diradical character of the LONS- ligand was predicted.

Arylamino radical complexes of ruthenium and osmium: dual radical counter in a molecule.

Radical and non-radical ruthenium and osmium complexes of 1-amino-9,10-anthraquinone (AqNH2), which is defined as a molecule of dual radical counter, are disclosed. 1-Amido-9,10-anthraquinone (AqNH-) complexes of the types trans-[RuII(AqNH-)(PPh3)2(CO)Cl] (1), trans-[OsII(AqNH-)(PPh3)2(CO)Br] (2) and trans-[RuIII(AqNH-)(PPh3)2Cl2] (3) were isolated. AqNH- of 1-3 is redox active and undergoes oxidation reversibly at +(0.05-0.35) V to the 1-amino-9,10-anthraquinone radical (AqNH˙) and reduction at -(0.86-1.60) V to the 1-amido-9,10-anthrasemiquinonate anion radical (AqNHSQ˙2-). The reaction of 2 with I2 in CH2Cl2 afforded a crystalline AqNH˙ complex of the type trans-[OsII(AqNH˙)(PPh3)2(CO)Br]+I5-·½I2 (2+I5-·½I2). AqNH˙ and AqNHSQ˙2- complexes of the types trans-[RuII(AqNH˙)(PPh3)2(CO)Cl]+ (1+), trans-[RuIII(AqNH˙)(PPh3)2Cl2]+ (3+), trans-[RuII(AqNHSQ˙2-)(PPh3)2(CO)Cl]- (1-) and trans-[OsII(AqNHSQ˙2-)(PPh3)2(CO)Br]- (2-) were generated chemically/electrochemically in solution. The electronic states of the complexes were authenticated by single crystal X-ray structure determinations of 1, 2·5/4 toluene, 3 and 2+I5-·½I2, EPR spectroscopy and density functional theory (DFT) calculations. AqNH˙ instigates a 2c-3e pπ-dπ interaction and the length in 2+I5-·½I2, 1.978(5) Å, is relatively shorter than the OsII-NHAq- length, 2.037(2) Å, while the Aq-NH˙ bond, 1.365(8) Å, is longer than the Aq-NH- bond, 1.328(3) Å. DFT calculations predicted that the atomic spin is delocalized over the ligand backbone (1+, 56%) particularly in one of the p-orbitals of the nitrogen and the metal atoms of the 1+ and 2+ ions, while the spin is dominantly localized on the anthraquinone fragment of the 1- and 2- ions. TD DFT calculations were employed to elucidate the origins of the lower energy absorption bands of the neutral complexes. Hypsochromic shifts of the UV-vis-NIR absorption maximum during 1→1+, 2→2+ and 3→3+ conversions were recorded by spectroelectrochemical measurements.

Radical and Non-Radical States of the [Os(PIQ)] Core (PIQ = 9,10-Phenanthreneiminoquinone): Iminosemiquinone to Iminoquinone Conversion Promoted o-Metalation Reaction.

The coordination and redox chemistry of 9,10-phenanthreneiminoquinone (PIQ) with osmium ion authenticating the [Os(II)(PIQ(•-))], [Os(III)(PIQ(•-))], [Os(III)(C,N-PIQ)], [Os(III)(PIQ)], and [Os(III)(PIQ(2-)) ] states of the [Os(PIQ)] core in the complexes of types trans-[Os(II)(PIQ(•-))(PPh3)2(CO)Br] (1), trans-[Os(III)(PIQ(•-))(PPh3)2Br2] (2), trans-[Os(III)(C,N-PIQ)(PPh3)2Br2]·2CH2Cl2 (3·2CH2Cl2), trans-[Os(III)(C,N-PIQ(Br))(PPh3)2Br2]·2CH2Cl2 (4·2CH2Cl2), trans-[Os(III)(C,N-PIQ(Cl2))(PPh3)2Br2] (6), trans-[Os(III)(PIQ(•-))(PPh3)2Br2](+)1/2I3(-)1/2Br(-) (1(+)1/2I3(-)1/2Br(-)), [Os(III)(PIQ)(PPh3)2Br2](+) (2(+)), and [Os(III)(PIQ(2-))(PPh3)2Br2](-) (2(-)) are reported (PIQ(•-) = 9,10-phenanthreneiminosemiquinonate anion radical; C,N-PIQ = ortho-metalated PIQ, C,N-PIQ(Br) = ortho-metalated 4-bromo PIQ, and C,N-PIQ(Cl2) = ortho-metalated 3,4-dichloro PIQ). Reduction of PIQ by [Os(II)(PPh3)3(H)(CO)Br] affords 1, while the reaction of PIQ with [Os(II)(PPh3)3Br2] furnishes 2. Oxidation of 1 with I2 affords 1(+)1/2I3(-)1/2Br(-), while the similar reactions of 2 with X2 (X = I, Br, Cl) produce the ortho-metalated derivatives 3·2CH2Cl2, 4·2CH2Cl2, and 6. PIQ and PIQ(2-) complexes of osmium(III), 2(+) and 2(-), are generated by constant-potential electrolysis. However, 2(+) ion is unstable in solution and slowly converts to 3 and partially hydrolyzes to trans-[Os(III)(PQ(•-))(PPh3)2Br2] (2PQ), a PQ(•-) analogue of 2. Conversion of 2(+) → 3 in solution excludes the formation of aryl halide as an intermediate for this unique ortho-metalation reaction at 295 K, where PIQ acts as a redox-noninnocent ambidentate ligand. In the complexes, the PIQ(•-) state where the atomic spin is more localized on the nitrogen atom is stable and is more abundant. The reaction of 2PQ, with I2 does not promote any ortho-metalation reaction and yields a PQ complex of type trans-[Os(III)(PQ)(PPh3)2Br2](+)I5(-)·2CH2Cl2 (5(+)I5(-)·2CH2Cl2). The molecular and electronic structures of 1-4, 6, 1(+), and 5(+) were established by different spectra, single-crystal X-ray bond parameters, cyclic voltammetry, and DFT calculations.

Radical non-radical states of the [Ru(PIQ)] core in complexes (PIQ = 9,10-phenanthreneiminoquinone).

9,10-Phenanthreneiminosemiquinonate anion radical (PIQ˙(-)) complexes of ruthenium of types trans-[Ru(II)(PIQ˙(-))(PPh3)2(CO)Cl] () and trans-[Ru(III)(PIQ˙(-))(PPh3)2Cl2] () are reported. Reactions of and with I2 afford trans-[Ru(III)(PIQ˙(-))(PPh3)2(CO)Cl](+)I3(-)·½CH2Cl2 ((+)I3(-)·½CH2Cl2) and trans-[Ru(PIQ˙(-))2(PPh3)2(µ-Cl)3](+)I3(-)·»I2·»toluene) ((+)I3(-)·»I2·»toluene), while the reaction of with Br2 yields a 9,10-phenanthreneiminoquinone (PIQ) complex of the type mer-[Ru(III)(PIQ)(PPh3)Br3]·½CH2Cl2 (·½CH2Cl2). In comparison, the reaction of trans-[Ru(III)(PQ˙(-))(PPh3)2Cl2] (PQ), a 9,10-phenanthrenequinone (PQ) analogue of affords only trans-[Ru(III)(PQ)(PPh3)2Cl2](+)Br3(-) ((+)Br3(-)). Considering the X-ray bond parameters, EPR spectra and the atomic spin densities obtained from the density functional theory (DFT) calculations, is defined as a PIQ˙(-) (average C-O/N and C-C lengths, 1.280(2) and 1.453(3) Å) complex of ruthenium(ii) while is a neutral PIQ (average C-O, C-N, C-C and C-O/N lengths, 1.248(7), 1.284(7), 1.485(8) and 1.266(7) Å) complex of the ruthenium(iii) ion. The single crystal X-ray bond parameters proposed that (+)I3(-) (average C-O/N and C-C lengths, 1.294(8) and 1.449(9) Å) and (average C-O/N and C-C lengths, 1.289(2) and 1.447(4) Å) are PIQ˙(-) complexes of ruthenium(iii), while the (+) ion (average C-O/N and C-C lengths, 1.288 ± 0.004 and 1.450 ± 0.017 Å) is a co-facial bi-octahedral complex of ruthenium(iii). In contrast, the (+) ion is a PQ complex of the ruthenium(iii) ion. EPR spectra and the calculated atomic spin densities authenticated that the (+) ion obtained after constant potential coulometric oxidation of is a PIQ complex of ruthenium(iii), while the (-) ion is a hybrid state of [Ru(II)(PIQ˙(-))] and [Ru(III)(PIQ(2-))] states. It is observed that the PIQ˙(-) state in which spin is more localized on the nitrogen (∼38% in and ∼35% in (-) ion) is stable and the coordination of the PIQ(2-) state is not observed in this study. Redox activities, UV-vis/NIR absorption spectra and their origins and the spectroelectrochemical measurements for → (+), → (-) and (+) → (2+) conversions are analyzed.

Zinc(II), iron(II/III) and ruthenium(II) complexes of o-phenylenediamine derivatives: oxidative dehydrogenation and photoluminescence.

Reactions of benzoyl pyridine, o-phenylenediamine and anhydrous ZnX2 in methanol afford imine complexes [Zn(L1)X2] (X = Cl, 1; X = Br, 2) in good yields (L1 = (E)-N(1)-(phenyl(pyridin-2-yl)methylene)benzene-1,2-diamine). The reduction of 1 with NaBH4 affords (E)-N(1)-(phenyl(pyridine-2-yl)methylene)benzene-1,2-diamine (L2H). The reaction of L2H with [Ru(II)(PPh3)3Cl2] results in the oxidative dehydrogenation to L1 generating cis-[Ru(II)(L1)(PPh3)Cl2] (3). The reaction of L2H with salicylaldehyde affords (E)-2-(((2-((phenyl(pyridin-2-yl)methyl)amino)phenyl)imino)methyl)phenol (L3H2). The reaction of L3H2 with anhydrous FeCl3 in CH3OH affords cis-[Fe(III)(L3H(-))Cl2] (4). Reaction of L3H2 with [Ru(II)(PPh3)3Cl2] results in the oxidative dehydrogenation to diimine, L4H, affording trans-[Ru(II)(L4(-))(PPh3)2](+), which is isolated as trans-[Ru(II)(L4(-))(PPh3)2]PF6 (5(+)PF6(-)) (L4H = 2-((E)-(2-((E)-phenyl(pyridin-2-yl)methyleneamino)phenylimino)methyl)phenol). The reduction of L3H2 with NaBH4 produces 2-(((2-((phenyl(pyridin-2-yl)methyl)amino)phenyl)amino)methyl)phenol (L5H3). With iron(III) L5H3 undergoes oxidative dehydrogenation to L3H2 affording 4, while with [Ru(II)(PPh3)3Cl2], L5H3 undergoes 4e + 4H(+) transfer giving 5(+). A fluid solution of L3H2 at 298 K exhibits an emission band at 470 nm (λ(ex) = 330 nm, τ1 = 3.70 ns) and a weaker band at 525 nm (λ(ex) = 330, 390 nm, τ1 = 1.1 ns) at higher concentrations due to molecular aggregation, which are temperature dependent. 4 is brightly emissive (λ(ex) = 330 nm, λ(em) = 450 nm, Φ = 0.586, τ1 = 3.70 ns). Time resolved emission spectra (TRES) and lifetime measurements confirm that the lower energy absorption band of L3H2 at 390 nm, which is absent in complex 4, has a larger non-radiative rate constant (k(nr)). The redox innocent Al(III) adduct of L3H2 is fluorescent (λ(ex) = 330 nm, λ(em) = 450 nm, τ1 = 3.70 ns). On the contrary, the cis-[Fe(II)(L3H(-))Cl2](-) and cis-[Co(L3H(-))Cl2](-) analogues are non emissive. Density function theory (DFT) calculations, redox potentials and the near infra-red (NIR) absorption data prove that 4 is emissive due to the stable [Fe(III)(L3H(-)*)] state, while 3, 5(+), cis-[Fe(II)(L3H(-))Cl2](-) and cis-[Co(L3H(-))Cl2](-) are non-emissive due to transformations of the [M(II)(L*)] to [M(III)(L˙(-)*)] states.