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High‐spin organic tetraradicals with significant intramolecular exchange interactions have high potential for advanced technological applications and fundamental research, but those synthesized to date possess limited stability and processability. In this work, we have designed a tetraradical based on the Blatter's radical and nitronyl nitroxide radical moieties and successfully synthesized it by using the palladium‐catalyzed cross‐coupling reaction of a triiodo‐derivative of the 1,2,4‐benzotriazinyl radical with gold(I) nitronyl nitroxide‐2‐ide complex in the presence of a newly developed efficient catalytic system. The molecular and crystal structure of the tetraradical was confirmed by X‐ray diffraction analysis. The tetraradical possesses good thermal stability with decomposition onset at ∼150 °C under an inert atmosphere and exhibits reversible redox waves at −0.54 and 0.45 V versus Ag/AgCl. The magnetic properties of the tetraradical were characterized by SQUID magnetometry of polycrystalline powders and EPR spectroscopy in various matrices. The collected data, analyzed by using high‐level quantum chemical calculations, confirmed that the tetraradical has a triplet ground state and a nearby excited quintet state. The unique high stability of the prepared triazinyl‐nitronylnitroxide tetraradical is a new milestone in the field of creating high‐spin systems. [ABSTRACT FROM AUTHOR]

This paper describes the stepwise aza‐Wittig reaction of 1,1′‐bis(triphenylphosphoranylidenamino)‐ferrocene with a paramagnetic isocyanate, namely, 3‐isocyanato‐2,2,5,5‐tetramethyl‐2,5‐dihydro‐1H‐pyrrole‐1‐oxyl, and then with substituted arylisocyanates. The intermediate product (a paramagnetic betaine), which is the product of an intramolecular nucleophilic attack of the nitrogen atom of the iminophosphorane moiety on the carbon atom of the carbodiimide functional group, was isolated and structurally characterized. Subsequent interaction of the betaine with arylisocyanates under mild conditions gave spin‐labeled ferrocenophanes with the 1,3‐diazetidine‐2,4‐diimine coupler. It was found that the mutual arrangement of the substituents in the latter depends on the nature of the substituents in the arylisocyanate. Iodophenyl derivatives of 1,3‐diazetidine‐2,4‐diimines were cross‐coupled with the gold(I) nitronyl nitroxide‐2‐ide complex, thus yielding diradicals: metallocenophanes functionalized with various types of nitroxide substituents. Molecular and crystal structures of all mono‐ and diradicals were solved by X‐ray diffraction analysis. [ABSTRACT FROM AUTHOR]

Two acceptor small molecules consisting of 2‐(11‐oxoanthra[2,1‐b]thiophen‐6‐ylidene)dipropanedinitrile frameworks connected by a bis(thiophen‐2‐ylethynyl)arene bridge were synthesized by the two‐step sequence of Sonogashira cross‐coupling and Knoevenagel condensation in order to investigate their performance as non‐fullerene acceptors in organic solar cells. Optical, electrochemical and photovoltaic properties of new 2,2′‐[2,2′‐(5,5′‐(arenediyl)bis(ethyne‐2,1‐diyl)bis(thien‐5,2‐diyl))bis(11‐oxoanthra[2,1‐b]thiophen‐6‐ylidene)]dipropanedinitriles and previously studied analogs of 2,2′‐[2,2′‐arenediylbis(11‐oxoanthra[1,2‐b]thiophene‐6‐ylidene)]dipropanedinitriles were compared to assess the effect of introducing ethynylthiophene units between the arene linker and the 2‐(11‐oxoanthrathiophen‐6‐ylidene)propanedinitrile units. Despite the proper energy level alignment and morphology, composites of the newly synthesized compounds with the PBDB‐T donor polymer demonstrate a moderate PCE of 0.54 %. The small value of the short circuit current as compared to composites with fullerene acceptors is probably due to the low electron mobility in the newly synthesized compounds. The low electron mobility, in turn, is probably cause by the LUMO localization at the edge units of the acceptor‐type molecules, in contrast to the almost uniform LUMO delocalization over the whole π‐conjugated system for high‐performing non‐fullerene acceptors such as ITIC. [ABSTRACT FROM AUTHOR]

The first example of a triply bridging (μ3‐P) phosphine ligand has been discovered in the crown‐shaped [Cu3(μ2‐Hal)3L] (Hal=Cl, Br, or I) complexes supported by tris[2‐(2‐pyridyl)ethyl]phosphine (L). Theoretical analysis completely confirms the observed μ3‐P‐bridging pattern, revealing the interaction of the same lone pair of phosphorus with three valence 4s‐orbitals of Cu atoms. The presented complexes exhibit outstanding blue phosphorescence (λem=442–465 nm) with the quantum efficiency reaching 100 %. The complex [Cu3(μ2‐I)3L] also exhibits remarkable thermo‐ and mechanochromic luminescence resulting in a sharp change in the emission colour upon external stimuli. These findings essentially contribute to coordination chemistry of the pnictine ligands. [ABSTRACT FROM AUTHOR]

While developing methods for obtaining high-spin graphene nanostructures, we carried out a model cross-coupling reaction between 1,8-diiodonaphthalene and an organogold derivative of a nitronyl nitroxide. It was found that only one iodine atom reacted, leading to the corresponding 8-iodonaphthalen-1-yl-substituted nitronyl nitroxide. The latter was successfully isolated as two polymorphic modifications, whose X-ray structural analysis revealed a strong distortion of the paramagnet's geometry in comparison with a noniodinated analog. Moreover, the spatial proximity of the heavy iodine atom and the paramagnetic moiety resulted in unprecedented temperature dynamics of the EPR spectrum. To clarify these dynamics, quantum chemical calculations were performed using the exact two-component relativistic X2C method with the self-consistent account of spin-orbit coupling in conjunction with the B3LYP functional and relativistic STO-type basis set. These computations predicted a reasonable aiso(127l) value that can affect the EPR spectrum. Substitution of the second iodine atom would lead to the formation of a diradical with a 1,8-naphthalenediyl bridge, whose structure and magnetic properties were analyzed at the DFT level. Two stable conformations of the diradical with strongly distorted geometry were identified. In both conformations, calculations predict a ferromagnetic exchange between the paramagnetic centers with J=8 and 14 cm-1 (H= -2 J·S1S2). [ABSTRACT FROM AUTHOR]

Interaction of the tetradentate redox‐active 6,6′‐[1,2‐phenylenebis(azanediyl)]bis(2,4‐di‐tert‐butylphenol) (H4L) with TeCl4 leads to neutral diamagnetic compound TeL (1) in high yield. The molecule of 1 has a nearly planar TeN2O2 fragment, which suggests the formulation of 1 as TeIIL2−, in agreement with the results of DFT calculations and QTAIM and NBO analyses. Reduction of 1 with one equivalent of [CoCp2] leads to quantitative formation of the paramagnetic salt [CoCp2]+[1].−, which was characterised by single‐crystal XRD. The solution EPR spectrum of [CoCp2]+[1].− at room temperature features a quintet due to splitting on two equivalent 14N nuclei. Below 150 K it turns into a broad singlet line with two weak satellites due to the splitting on the 125Te nucleus. Two‐component relativistic DFT calculations perfectly reproduce the a(14N) HFI constants and A∥(125Te) value responsible for the low‐temperature satellite splitting. Calculations predict that the additional electron in 1.− is localised mainly on L, while the spin density is delocalised over the whole molecule with significant localisation on the Te atom (≥30 %). All these data suggest that 1.− can be regarded as the first example of a structurally characterised monomeric tellurium–nitrogen radical anion. [ABSTRACT FROM AUTHOR]

Thermally stable organic diradicals with a triplet ground state along with large singlet‐triplet energy gap have significant potential for advanced technological applications. A series of phenylene‐bridged diradicals with oxoverdazyl and nitronyl nitroxide units were synthesized via a palladium‐catalyzed cross‐coupling reaction of iodoverdazyls with a nitronyl nitroxide‐2‐ide gold(I) complex with high yields. The diradicals exhibit high stability and do not decompose in an inert atmosphere up to 180 °C. For the diradicals, both substantial AF (ΔEST≈−64 cm−1) and FM (ΔEST≥25 and 100 cm−1) intramolecular exchange interactions were observed. The sign of the exchange interaction is determined both by the bridging moiety (para‐ or meta‐phenylene) and by the type of oxoverdazyl block (C‐linked or N‐linked). Upon crystallization, diradicals with the triplet ground state form unique one‐dimensional exchange‐coupled chains with strong intra‐ and weak inter‐diradical ferromagnetic coupling. [ABSTRACT FROM AUTHOR]

By means of cyclic voltammetry (CV) and DFT calculations, it was found that the electron‐acceptor ability of 2,1,3‐benzochalcogenadiazoles 1–3 (chalcogen: S, Se, and Te, respectively) increases with increasing atomic number of the chalcogen. This trend is nontrivial, since it contradicts the electronegativity and atomic electron affinity of the chalcogens. In contrast to radical anions (RAs) [1].− and [2].−, RA [3].− was not detected by EPR spectroscopy under CV conditions. Chemical reduction of 1–3 was performed and new thermally stable RA salts [K(THF)]+[2].− (8) and [K(18‐crown‐6)]+[2].− (9) were isolated in addition to known salt [K(THF)]+[1].− (7). On contact with air, RAs [1].− and [2].− underwent fast decomposition in solution with the formation of anions [ECN]−, which were isolated in the form of salts [K(18‐crown‐6)]+[ECN]− (10, E=S; 11, E=Se). In the case of 3, RA [3].− was detected by EPR spectroscopy as the first representative of tellurium–nitrogen π‐heterocyclic RAs but not isolated. Instead, salt [K(18‐crown‐6)]+2[3‐Te2]2− (12) featuring a new anionic complex with coordinate Te−Te bond was obtained. On contact with air, salt 12 transformed into salt [K(18‐crown‐6)]+2[3‐Te4‐3]2− (13) containing an anionic complex with two coordinate Te−Te bonds. The structures of 8–13 were confirmed by XRD, and the nature of the Te−Te coordinate bond in [3‐Te2]2− and [3‐Te4‐3]2− was studied by DFT calculations and QTAIM analysis. Heterocyclic radical anions: Chemical reduction of 2,1,3‐benzochalcogenadiazoles 1–3 (chalcogen=S, Se, Te, respectively) afforded new thermally stable radical anion (RA) salts [K(THF)]+[2].− and [K(18‐crown‐6)]+[2].− in addition to known salt [K(THF)]+[1].−, whereas RA [3].− was detected by EPR as the first Te–N π‐heterocyclic RA but not isolated; instead, salt [K(18‐crown‐6)]+2[3‐Te2]2− (12) featuring a new anionic complex with coordinate Te−Te bond was obtained (see figure). [ABSTRACT FROM AUTHOR]

Abstract: Donor–acceptor (D–A) complexes between 3,4‐dicyano‐1,2,5‐chalcogenadiazoles [chalcogen=Te (1 a), Se (1 b), S (1 c)] and the pseudohalides CN− and XCN− (X=O, S, Se, Te) were studied experimentally and theoretically. For 1 a, they were isolated as [K(18‐crown‐6)][1 a‐CN] (2), [K(18‐crown‐6)][1 a‐NCO] (3), [K(18‐crown‐6)][1 a‐SCN] (4), [K(18‐crown‐6)][1 a‐SeCN] (5), and [K][1 a‐NCSe] (6) and characterized by X‐ray diffraction (XRD), UV/Vis and NMR spectroscopy, and DFT and QTAIM calculations. For 1 b and 1 c, the complexes were not isolated due to unfavorable thermodynamics. In all isolated complexes, the D–A bonds, stabilized by negative hyperconjugation, were longer than the sum of the covalent radii and shorter than the sum of the van der Waals radii of the bonded atoms. In mixtures of 1 a, F−, and SeCN−, the complex [1 a‐F]− was selectively formed in accordance with thermodynamics. The reaction of 1 a with SeCN− and the cyclic trimeric perfluoro‐ortho‐phenylene mercury afforded the complex [K(18‐crown‐6)][SCN]⋅(o‐C6F4Hg)3, which was characterized by XRD. [ABSTRACT FROM AUTHOR]

A new approach to the synthesis of fused 1,2,3-thiaselenazoles-rare five-membered heterocycles that contain two different chalcogens-from the corresponding 1,2,3-dithiazoles and SeO2 was accomplished by selective exchange of S and Se atoms. The fused carbo- and heterocyclic units were indene, naphthalenone, cyclohexadienone, cyclopentadiene, benzoannulene, and benzoxazine. The molecular structures of two of the thiaselenadiazole products and one of the dithiazole precursors were confirmed by single-crystal X-ray diffraction. The reaction is highly solvent selective; it only takes place in solvents that contain a C=O group (e.g., DMF or tetramethylurea). According to DFT calculations, the reaction is thermodynamically favorable. Based on the DFT calculations and 77Se NMR spectroscopy, two tentative mechanisms that feature isomeric transition states and intermediates are suggested for the reaction via ring-opening addition of SeO2 to the S−X dithiazole bond (X=N or S). The DFT-calculated first adiabatic electron affinities of the compounds were chalcogen independent and positive in all cases, which assumes formation of thermodynamically stable radical anions (RAs). These calculated RAs featured either normal or abnormal elongation of the S1−X2 (X=S or Se) bond relative to their neutral precursors and possessed π* or σ* SOMOs, respectively. [ABSTRACT FROM AUTHOR]

The first lanthanide complexes with a redox-active sulfur diimide ligand, [LnCp*2(Me3SiN=)2S] (Ln=Sm, Eu, Yb; Cp*=η5-C5Me5), are reported. The complexes were synthesized by using [LnCp*2(THF)2] and (Me3SiN=)2S and have been thoroughly characterized by single-crystal X-ray diffraction, EPR spectroscopy, UV/Vis/NIR electronic absorption spectroscopy and SQUID magnetometry. The results, as interpreted by CASSCF/SOC-RASSI calculations providing a non-perturbative treatment of spin-orbit coupling, indicate that these paramagnetic complexes are best described as Ln3+ and [(Me3SiN=)2S]− . adducts. As such, these complexes contain the first isolated and structurally characterized acyclic [(RN=)2S]− . radical anions. [ABSTRACT FROM AUTHOR]

The first lanthanide complexes with a redox-active sulfur diimide ligand, [LnCp*2(Me3SiN=)2S] (Ln=Sm, Eu, Yb; Cp*=η5-C5Me5), are reported. The complexes were synthesized by using [LnCp*2(THF)2] and (Me3SiN=)2S and have been thoroughly characterized by single-crystal X-ray diffraction, EPR spectroscopy, UV/Vis/NIR electronic absorption spectroscopy and SQUID magnetometry. The results, as interpreted by CASSCF/SOC-RASSI calculations providing a non-perturbative treatment of spin-orbit coupling, indicate that these paramagnetic complexes are best described as Ln3+ and [(Me3SiN=)2S]− . adducts. As such, these complexes contain the first isolated and structurally characterized acyclic [(RN=)2S]− . radical anions. [ABSTRACT FROM AUTHOR]

The design and synthesis of novel charge-transfer (CT) complexes are of interest for fundamental chemistry and applications to materials science. In addition to the recently described first CT complex with both electron acceptor (A) and donor (D) groups belonging to the 1,2,5-thiadiazole series ( 1; A: 4-nitro-2,1,3-benzothiadiazole; D: 4-amino-2,1,3-benzothiadiazole), herein novel CT complexes 2 and 3 with 1,2,5-thiadiazoles as both A (4,6-dinitro-2,1,3-benzothiadiazole and [1,2,5]thiadiazolo[3,4- c][1,2,5]thiadiazole) and D (4-amino-2,1,3-benzothiadiazole) were synthesized. The series is completed by complex 4 with [1,2,5]thiadiazolo[3,4- c][1,2,5]thiadiazole as A and phenoxatellurine as D. Structures of complexes 2- 4 were characterized by single-crystal X-ray diffraction (XRD), as well as solution and solid-state UV/Vis spectroscopy. Thermodynamics of their formation were obtained by density functional theory (DFT) calculations, their bonding situations were analyzed by quantum theory of atoms in molecules (QTAIM) calculations and dimer model energies of interactions quantified in the framework of the Hirshfeld surface (HS) analysis. With DFT calculations, the largest value of CT between D and A was found for complex 2, with 0.027 e in the XRD structure and 0.150 e in the optimized structure in MeCN. In the UV/Vis spectra, the λmax of the CT bands of 2- 4 varied in the range λ=517-705 nm. Model energy calculations for 1- 4 revealed the importance of both dispersion interactions and hydrogen bonding between D and A as contributors to CT in the crystalline state. In an attempt to enlarge the CT value with bis[1,2,5-thiadiazolo][3,4- b;3′,4′- e]pyrazine as A and 4-amino-2,1,3-benzoselenadiazole as D, an unprecedented 1:1 addition reaction was observed upon formation of a C−N bond between atom C7 of D and pyrazine atom N4 of A, accompanied by hydrogen atom transfer from C7 to another pyrazine atom N8 (compound 5). According to DFT calculations, the reaction is a multistep process featuring diradical intermediates and hydrogen atom intramolecular migration over four positions. Molecular and crystal structures of 5 (solvate with toluene) were elucidated by XRD and the crystal structure revealed a rather unusual porous framework. [ABSTRACT FROM AUTHOR]

It was shown that dipole-stabilized paramagnetic carbanion lithiated 4,4,5,5-tetramethyl-4,5-dihydro-1 H-imidazol-1-oxyl 3-oxide can be attached in a nucleophilic manner to either isolated or conjugated aldonitrones of the 2,5-dihydroimidazole 3-oxide and 2 H-imidazole 1-oxide series to afford adducts the subsequent oxidation of which leads to polyfunctional mono- and diradicals. According to XRD, at least two polymorphic modifications can be formed during crystallization of the resulting paramagnetic compounds, and for each of them, geometric parameters of the molecules are similar. An EPR spectrum of the diradical in frozen toluene has a complicated lineshape, which can be fairly well reproduced by using X-ray diffraction structural analysis and the following set of parameters: D=14.9 mT, E=1.7 mT; tensor a(14N)=[0.260 0.260 1.625] mT, two equivalent tensors for the nitronyl nitroxide moiety a(14N)=[0.198 0.198 0.700] mT, and g≈2.007. According to our DFT and ab initio calculations, the intramolecular exchange in the diradical is very weak and most likely ferromagnetic. [ABSTRACT FROM AUTHOR]

The reactions of [Mn4(hmp)6(NO3)2(H2O)2](ClO4)2 with (Bu4N)2[CoX4] (X = Cl, Br) in CH3CN have been studied and the new heterometallic tetranuclear clusters [CoIII2MnII2(hmp)6Cl2(CH3CN)2]MnIICl4 ·3CH3CN and [CoIII2MnII2(hmp)6Br2(CH3CN)2]MnIIBr4 ·4CH3CN have been synthesized and characterized by TGA, electrospray ionization mass spectrometry, single-crystal X-ray diffraction, and magnetic measurements. The magnetic properties of the heterometallic clusters were analyzed by DFT and ab initio calculations. [ABSTRACT FROM AUTHOR]

The photochemistry of pivaloyl, benzoyl, 4-phenylbenzoyl, and 2-anthroyl azides has been studied using femtosecond (fs) time-resolved infrared (TRIR) and UV-vis spectroscopy and interpreted with the aid of computational chemistry. Density functional theory calculations revealed a significant difference in the nature of the lowest singlet excited state for these carbonyl azides. The lowest singlet excited states ( S1) of p-phenylbenzoyl and 2-anthroyl azides are (π,π*) in nature, while the pivaloyl and benzoyl azides S1 states involve ( n,π*) excitations. Nevertheless, for all acyl azides studied here, a similar, and intense, IR band at about 2100 cm−1 has been detected in the ultrafast TRIR experiments following 270 nm excitation. These bands were shifted to lower energy by about 100 cm−1 relative to the N3 stretching mode for the ground states of these azides. These 2100 cm−1 vibrational bands were assigned to the S1 states of acyl azides in agreement with density functional theory calculations. The decay of the acyl azide S1 states was described by bi-exponential functions. The fast component was attributed to the decay of the hot S1 state and the longer component to the decay of the thermally relaxed S1 state. A strong and broad transient absorption in the 350-650 nm spectral range was observed in the fs UV-vis experiments for p-phenylbenzoyl and 2-anthroyl azides. The carrier of this absorption also decayed bi-exponentially, and the time constants were in excellent agreement with those found in the fs TRIR experiments. The slow component of the S1 state decay was found to be dependent on the solvent polarity. When the lifetime of the acyl azide S1 state is substantially longer than the time constant for vibrational cooling of nascent (hot) isocyanate, the correlation between the S1 decay and isocyanate formation was clear. The 270 nm excitation populates the Sn ( n ≥ 2) states of these acyl azides. It was established that a hot nitrene is produced more efficiently from both the Sn and hot S1 states than from the relaxed S1 state of these acyl azides. Thus, time-resolved study provides direct experimental evidence that the S1 state is the precursor of nitrene only when the S1 state is pumped directly and when the S1 state lifetime is longer than the time constant of vibrational cooling of the newborn nitrene. All of these results are consistent with the data obtained recently for 2-napththoyl azide. Copyright © 2012 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

In comparison with 2,1,3-benzothia(selena)diazoles, electrochemical oxidation and reduction of their 4,5,6,7-tetrafluoro derivatives and a number of related compounds were studied by cyclic voltammetry. For nine examples of this class, the first reduction peaks are reversible and corresponding radical anions (RAs) are long-lived at 295 K in MeCN and especially in DMF. The oxidation peaks were irreversible and corresponding radical cations were not observed. Electrochemically generated RAs were characterized by EPR measurements and DFT calculations at the UB3LYP/6-31+G(d) level. The spin density distribution in the RAs is analyzed in connection with effects of S substitution by Se and/or H by F. The prospects of the studied RAs in the design and synthesis of magnetically active materials are discussed. Copyright © 2010 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

Ferrocenophanes, Nitroxide diradicals, Wittig reactions, EPR spectroscopy, DFT calculations Keywords: Ferrocenophanes; Nitroxide diradicals; Wittig reactions; EPR spectroscopy; DFT calculations EN Ferrocenophanes Nitroxide diradicals Wittig reactions EPR spectroscopy DFT calculations 1 1 1 02/21/22 20220218 NES 220218 B The Cover Feature b shows a beautiful sunrise metaphorically representing the boundary between chemistry and physics, the interaction of which has paved the way for the synthesis of a biradical with a ferrocene-derived inflexible bridging moiety. Cover Feature: Multispin Systems with a Rigid Ferrocene-1,1'-diyl-Substituted 1,3-Diazetidine-2,4-diimine Coupler: A General Approach (Eur. J. Org. [Extracted from the article]

The dioxolene type ligands (Diox) derived from ortho‐quinones are the most widely studied redox noninnocent ligands existing in the dianionic (Cat), anion radical (SQ) or neutral (Q) forms although a highly delocalized electronic structure is also possible. For [ReO(Diox)2PPh3]− (2) and [ReCl3(Diox)PPh3] (3) complexes, the ReV‐Cat2 and ReIV‐SQ localized valence states were proposed on the basis of their XRD structures. To understand in detail the electronic structure of these complexes, we performed a series of the all‐electron calculations at the DKH2‐CASSCF/CASPT2 and DKH2‐CASSCF/NEVPT2 levels taking into account scalar relativistic and spin‐orbit effects. All calculations predicted that 2 has a singlet ground state with a predominant contribution of a single electronic configuration with doubly occupied molecular orbitals being pure o‐quinone LUMOs of both Diox ligands that corresponds to the ReV‐Cat2 valence state. Complex 3 has a triplet ground state with four electronic configurations contributing mainly into its wavefunction and differing by the occupation of bonding and antibonding combinations of the o‐quinone LUMO and rhenium d‐AO with nearly equal contributions. This leads to the empirical "metrical oxidation state" of dioxolene ligand being −1 that is usually referred to the ReIV‐SQ oxidation state. However, in fact, the negative charge on the Diox ligand is mainly provided by a pair of electrons on the bonding MO. The standard DFT calculations entirely fail to correctly predict the ground state multiplicity for 3. [ABSTRACT FROM AUTHOR]

Redox‐Active Sulphur Diimide Ligand Anion radicals of R−N=S=N−R have never been isolated or structurally characterized. In their Full Paper on page 1278 ff., N P. Gritsan, R. T. Boeré, P. W. Roesky, A. V. Zibarev, S. N. Konchenko et al. report the first Cp*2Ln complexes (Ln = Sm, Eu, Yb; R = NSiMe3) of sulphur diimides and demonstrate by exhaustive characterisation (X‐ray diffraction, EPR, UV‐Vis‐NIR spectroscopy, SQUID magnetometry and rigorous ab initio computational methods) that these powerful reducing agents transfer an electron to the coordinated thiazyl ligand. A brand new world of redox non‐innocent ligands has thus emerged on the horizon. [ABSTRACT FROM AUTHOR]

Redox‐Active Sulphur Diimide Ligand Anion radicals of R−N=S=N−R have never been isolated or structurally characterized. In their Full Paper on page 1278 ff., N P. Gritsan, R. T. Boeré, P. W. Roesky, A. V. Zibarev, S. N. Konchenko et al. report the first Cp*2Ln complexes (Ln = Sm, Eu, Yb; R = NSiMe3) of sulphur diimides and demonstrate by exhaustive characterisation (X‐ray diffraction, EPR, UV‐Vis‐NIR spectroscopy, SQUID magnetometry and rigorous ab initio computational methods) that these powerful reducing agents transfer an electron to the coordinated thiazyl ligand. A brand new world of redox non‐innocent ligands has thus emerged on the horizon. [ABSTRACT FROM AUTHOR]