Gradual solid-state redox-isomerism in the lanthanide series.

Oxidation of [(ArBIG-bian)2-Yb2+(dme)] (1) (ArBIG-bian = 1,2-bis[(2,6-dibenzhydryl-4-methylphenyl)imino]acenaphthene; dme = 1,2-dimethoxyethane) by 0.5 equivalent of Me2NC(S)S-S(S)CNMe2 in dme at ambient temperature affords a mixture of two products, [(ArBIG-bian)2-Yb3+{SC(S)NMe2}1-(dme)] and [(ArBIG-bian)1-Yb2+{SC(S)NMe2}1-(dme)], which represent two redox-isomers (2a and 2b, respectively). Their ratio in solution depends on the solvent as well as on the temperature. In the solid state, a decrease of temperature (350 → 100 K) caused an electron transfer from the Yb2+ ion to the ArBIG-bian radical-anion in isomer 2b to afford isomer 2a. Accordingly, the ratio of isomers 2a and 2b changes from 1 : 1 (350 K) to 3 : 1 (100 K). In contrast, in the dimer [(dme)(dpp-bian)1-Yb2+(µ-Cl)2Yb3+(dpp-bian)2-(dme)] (dpp-bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene), which is the sole example of a lanthanide complex that reveals solid-state redox-isomerism (valence tautomerism) reported so far, the electron transfer from the Yb2+ ion to the dpp-bian radical-anion takes place at around 150 K and is completed within a temperature interval of ca. 7 K.

Valence tautomeric interconversion of bis-dioxolene cobalt complex with imino-pyridine functionalized by TEMPO moiety in solid solutions with isostructural nickel analogue: phase transitions and monocrystal destruction.

Valence tautomeric complexes (VT) are promising systems for creating molecular devices. From this viewpoint, valence tautomeric complexes with a hysteresis loop on the magnetic curve are of special interest as potential memory elements. The hysteresis loop is a consequence of retarded structural rearrangements which investigation is an actual problem. Recently, we have described a new VT transition taking place in a bis-dioxolene cobalt complex with imino-pyridine having a TEMPO substituent (A. A. Zolotukhin, et al., Inorg. Chem., 2017, 56, 14751-14754). Valence tautomeric transformation occurs with a hysteresis loop and is accompanied by a phase transition. The phase transition taking place during cooling is accompanied by crystal destruction. This fact makes it impossible to monitor the structural changes responsible for the hysteresis loop. The current research attempts to resolve this problem. A nickel compound of the same composition (TEMPO-imino-pyridine)Ni(3,6-DBSQ)2 was synthesized and characterized. It was established to be isostructural with the cobalt complex. It was used as an inert matrix for the dilution of the VT cobalt complex. The number of solid solutions with Co/Ni ratios of 1 : 1, 1 : 2, 1 : 4, and 1 : 8 was obtained. Variable temperature magnetic susceptibility measurements show that VT transformation with a hysteresis loop takes place in all solid solutions. The hysteresis loop is shifted to low temperatures primarily due to the shifting of its low-temperature boundary with dilution. The hysteresis width does not change significantly with dilution. DSC detected that transformations are accompanied by phase transitions at different temperatures at cooling and heating. The phase transition at the first cooling occurs at slightly lower temperatures compared with subsequent cycles. These temperatures correspond to the transition temperatures detected from the magnetic curves. The phase transition during the first cooling is accompanied by crystal destruction. Physical destruction takes place in the crystals of all solid solutions. X-ray diffraction powder patterns confirm that phase transition is accompanied by considerable reorganization of the crystal structure typical for the first order transitions. The unit cell volume of solid solutions is larger than that of pure complexes. Especially calculated crystal invariom indicated that the "lattice energy" in a solid solution is the lowest compared with that in "pure" nickel and cobalt complexes.

Diversity of transformation of heteroallenes on acenaphthene-1,2-diimine aluminum oxide.

The reactions of oxide [(dpp-bian)Al(µ2-O)2Al(dpp-bian)] (1) (dpp-bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene) with phenyl- or cyclohexylisocyanates result in the formation of carbonimidate derivatives [(dpp-bian)Al(µ-O)(µ-RNCO2)Al(dpp-bian)] (R = Ph, 2; Cy, 3). Addition of N,N'-dicyclohexylcarbodiimide to compound 1 leads to the formation of ureate complex [(dpp-bian)Al(µ-O)(µ-(CyN)2CO)Al(dpp-bian)] (4). The reactions of the oxide 1 with pinacolborane and catecholborane afford oxo-bridged hydride [{(dpp-bian)Al(H)}(µ-O){Al(OBpin)(dpp-bian)}] (5) and compound [{(dpp-bian)Al(OBCat)}2(µ-O)] (7), respectively. Insertion of cyclohexylisocyanate into the Al-H bond of compound 5 gives CO insertion product [{(dpp-bian)Al(OC(H)NCy)}(µ-O){Al(OBpin)(dpp-bian)}] (6). New compounds have been characterized by ESR and IR spectroscopy; their molecular structures have been established by single-crystal X-ray analysis. The oxide 1 serves as a catalyst for the hydroboration of heteroallenes (isocyanates, carbodiimides) with pinacolborane.

Lanthanide Coordination Polymers with Soft-Base Ditopic Bisthiazolate Ligands.

In order to prepare the first lanthanide coordination polymers (CPs) based on ditopic sulfide ligands, benzo[1,2-d:4,5-d']bisthiazole-2,6(3H,7H)-dithione (H2L) was used as a linker. The reactions of lanthanide silylamides Ln[N(SiMe3)2]3 (Ln = Nd, Gd, Er, and Yb) with H2L result in the formation of soluble dimethyl sulfoxide (DMSO) ionic salts [Ln(DMSO)8][L]1.5 [Ln = Nd (1), Gd (2), Er (3), and Yb (4)]. Due to the lack of coordination of anionic ligands, compounds 1, 3, and 4 do not show sensitized metal-centered photoluminescence (PL), while Gd compound 2 shows weak phosphorescence at 77 K. It was found that the heating of 1 in a 1:9 DMSO/1,4-dioxane mixture leads to the formation of large crystals of 2D CP [Nd(DMSO)3L1.5·0.5diox]n (5), where deprotonated dithione H2L plays the role of a ditopic linker. This linker acts as an "antenna" in compound 5, providing an intense near-infrared (NIR) PL of Nd3+ ion upon near-UV and blue-light excitation. The application of a synthetic protocol similar to that of compounds 2-4 led to the formation of amorphous compounds [Ln(DMSO)3L1.5·0.5diox]n [Ln = Gd (6), Er (7), and Yb (8)], whose PL properties significantly differ from those of the parental ionic salts. In the case of Yb polymer 8, the PL excitation spectra are shifted to the red region due to a low-energy ligand-to-metal charge-transfer state. The synthesized compounds 5-8 are the first examples of lanthanide CPs using soft-base ditopic linkers in their structures.

Praseodymium Metallacrown-Based NMR Probe for Enantioselective Discrimination of Mandelate Anions in Water.

Recently, the enhanced interest in water-soluble aminohydroximate Ln(III)-Cu(II) metallacrowns (MC) is largely due to their fascinating structural chemistry, diverse properties and ease of synthesis. We examined the water-soluble praseodymium(III) alaninehydroximate complex Pr(H2O)4[15-MCCu(II)Alaha-5]·3Cl (1) as a highly effective chiral lanthanide shift reagent for NMR analysis of the biologically relevant (R/S)-mandelate (MA) anions in aqueous media. The R-MA and S-MA enantiomers can be easily discriminated in the presence of small (1.2-6.2 mol %) amounts of MC 1 by the 1H NMR signals of multiple protons exhibiting an enantiomeric shift difference (ΔΔδ) of 0.06 ppm up to 0.31 ppm. Additionally, a possibility of coordination of MA to the metallacrown was investigated by the ESI-MS technique and a Density Functional Theory modeling of the molecular electrostatic potential and noncovalent interactions.

Synthesis and Antimicrobial Activity of Sulfenimines Based on Pinane Hydroxythiols.

The widespread presence of multidrug-resistant pathogenic microorganisms challenges the development of novel chemotype antimicrobials, insensitive to microbial tools of resistance. To date, various monoterpenoids have been shown as potential antimicrobials. Among many classes of molecules with antimicrobial activity, terpenes and terpenoids are an attractive basis for the design of antimicrobials because of their low toxicity and availability for various modifications. In this work, we report on the synthesis of sulfenimines from chiral trifluoromethylated and non-fluorinated pinane-type thiols. Final compounds were obtained with yields of up to 81%. Among the 13 sulfenimines obtained, 3 compounds were able to repress the growth of both bacteria (S. aureus, both MSSA and MRSA; P. aeruginosa) and fungi (C. albicans) with an MIC of 8-32 µg/mL. Although compounds exhibited relatively high cytotoxicity (the therapeutic index of 3), their chemotype can be used as a starter point for the development of disinfectants and antiseptics for targeting multidrug-resistant pathogens.

Synthesis of Trifluoromethylated Monoterpene Amino Alcohols.

For the first time, monoterpene trifluoromethylated ß-hydroxy-benzyl-O-oximes were synthesized in 81-95% yields by nucleophilic addition of the Ruppert-Prakash reagent (TMSCF3) to the corresponding ß-keto-benzyl-O-oximes based on (+)-nopinone, (-)-verbanone and (+)-camphoroquinone. Trifluoromethylation has been determined to entirely proceed chemo- and stereoselective at the C=O rather than C=N bond. Trifluoromethylated benzyl-O-oximes were reduced to the corresponding α-trifluoromethyl-ß-amino alcohols in 82-88% yields. The structure and configuration of the compounds obtained have been established.

Synthesis and Biological Activity of Unsymmetrical Monoterpenylhetaryl Disulfides.

New unsymmetrical monoterpenylhetaryl disulfides based on heterocyclic disulfides and monoterpene thiols were synthesized for the first time in 48-88% yields. Hydrolysis of disulfides with fragments of methyl esters of 2-mercaptonicotinic acid was carried out in 73-95% yields. The obtained compounds were evaluated for antioxidant, antibacterial, antifungal activity, cytotoxicity and mutagenicity.

Reduction of CO2 with Aluminum Hydrides Supported with Ar-BIAN Radical-Anions (Ar-BIAN = 1,2-Bis(arylimino)acenaphthene).

The reactions of H2AlCl with [(dpp-Bian)Na(Et2O)n] and [(ArBIG-Bian)Na(THF)] produce respective aluminum hydrides supported by radical-anionic 1,2-bis(arylimino)acenaphthene ligands, [(dpp-Bian)AlH2] (1) and [(ArBIG-Bian)AlH2(THF)] (2) (dpp-Bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene); ArBIG-Bian = 1,2-bis[(2,6-dibenzhydryl-4-methylphenyl)imino]acenaphthene). The reaction of 1 with CO2 proceeds with reduction of both C═O bonds and results in diolate [{(dpp-Bian)Al(µ-O2CH2)}2] (3). Complex 2 reacts with CO2 to carbonate [{(ArBIG-Bian)Al(µ-OCH2OCO2)}2] (4) that is a result of the insertion of CO2 into the Al-O bond in diolate species formed initially. Aluminum monohydrides [(dpp-Bian)AlH(X)] (X = Cl, 5; Me, 6) react with CO2 to form respective alumoxanes [{(dpp-Bian)AlX}2(µ-O)] (X = Cl, 7 and X = Me, 8). Compounds 1-4, 7, and 8 have been characterized by ESR and IR spectroscopy, and their molecular structures have been determined by single-crystal X-ray analysis.

Novel Oxidovanadium Complexes with Redox-Active R-Mian and R-Bian Ligands: Synthesis, Structure, Redox and Catalytic Properties.

A new monoiminoacenaphthenone 3,5-(CF3)2C6H3-mian (complex 2) was synthesized and further exploited, along with the already known monoiminoacenaphthenone dpp-mian, to obtain oxidovanadium(IV) complexes [VOCl2(dpp-mian)(CH3CN)] (3) and [VOCl(3,5-(CF3)2C6H3-bian)(H2O)][VOCl3(3,5-(CF3)2C6H3-bian)]·2.85DME (4) from [VOCl2(CH3CN)2(H2O)] (1) or [VCl3(THF)3]. The structure of all compounds was determined using X-ray structural analysis. The vanadium atom in these structures has an octahedral coordination environment. Complex 4 has an unexpected structure. Firstly, it contains 3,5-(CF3)2C6H3-bian instead of 3,5-(CF3)2C6H3-mian. Secondly, it has a binuclear structure, in contrast to 3, in which two oxovanadium parts are linked to each other through V=O···V interaction. This interaction is non-covalent in origin, according to DFT calculations. In structures 2 and 3, non-covalent π-π staking interactions between acenaphthene moieties of the neighboring molecules (distances are 3.36-3.40 Å) with an estimated energy of 3 kcal/mol were also found. The redox properties of the obtained compounds were studied using cyclic voltammetry in solution. In all cases, the reduction processes initiated by the redox-active nature of the mian or bian ligand were identified. The paramagnetic nature of complexes 3 and 4 has been proven by EPR spectroscopy. Complexes 3 and 4 exhibited high catalytic activity in the oxidation of alkanes and alcohols with peroxides. The yields of products of cyclohexane oxidation were 43% (complex 3) and 27% (complex 4). Based on the data regarding the study of regio- and bond-selectivity, it was concluded that hydroxyl radicals play the most crucial role in the reaction. The initial products in the reactions with alkanes are alkyl hydroperoxides, which are easily reduced to their corresponding alcohols by the action of triphenylphosphine (PPh3). According to the DFT calculations, the difference in the catalytic activity of 3 and 4 is most likely associated with a different mechanism for the generation of ●OH radicals. For complex 4 with electron-withdrawing CF3 substituents at the diimine ligand, an alternative mechanism, different from Fenton's and involving a redox-active ligand, is assumed.

Metal-Organic Frameworks Derived from Calcium and Strontium Complexes of a Redox-Active Ligand.

The reactions of monomeric [(dpp-Bian)M(thf)4] (M = Ca (1a), Sr (1b); dpp-Bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene) with 4,4'-bipyridyl (4,4'-bipy) proceed with electron transfer from dpp-Bian2- to 4,4'-bipy0 to afford calcium and strontium complexes containing simultaneously radical-anionic dpp-Bian- and 4,4'-bipy- ligands. In tetrahydrofuran (thf) the reactions result in 1D coordination polymers [{(dpp-Bian)M(4,4'-bipy)(thf)2}·4thf]n (M = Ca (2a), Sr (2b)), while in a thf/benzene mixture the reaction between 1a and 4,4'-bipy affords the 2D metal-organic framework [{(dpp-Bian)Ca(4,4'-bipy)2}·2thf·2C6H6]n (3). The structures of compounds 2a,b and 3 have been determined by single-crystal X-ray analyses. The presence of the ligand-localized unpaired electrons allows the use of ESR spectroscopy for characterization of the compounds 2a,b and 3. DFT calculations of model calcium complexes with the dpp-Bian, 4,4'-bipy, and thf ligands confirm the energetically favorable open-shell configurations of the molecules bearing the 4,4'-bipy fragments. The magnetic susceptibility measurements confirm the presence of two unpaired electrons per monomeric unit in 2a,b and 3. The thermal stability of compounds 2a,b and 3 was studied by thermogravimetric analysis (TGA). To the best of our knowledge, 3 is the first MOF simultaneously containing two different paramagnetic bridging ligands inside the framework.

Single Crystal X-ray Diffraction Studies of Two Polymorphic Modifications of the Dicarbonyl-o-Semiquinonato Rhodium Complex at Different Temperatures. Destruction Stimulated by Cooling Versus Stability.

It was found that the dicarbonyl-rhodium-o-semiquinonate complex (which thread-like crystals can bend reversibly under light/warm activation) can form two polymorphic modifications: isometric prisms (1) and sticks (2). Some thin sticks can bend as mentioned above. X-ray diffraction studies of polymorphic modifications at different temperatures were carried out. It was found that crystals 1 are destructed after cooling to 110 K as opposed to crystals 2. In turn, the reversible phase transition is detected in 2. In both polymorphic modifications, stack packaging motifs through the direct Rh-Rh bond are observed. The principal difference between packages of polymorphic modifications is that molecules 1 in the adjacent stacks are shifted relative to each other along the stack, in contrast to crystal 2. It was found that different packing of stacks leads to different anisotropic compression of crystals 1 and 2 during cooling, which is a key factor of their stability. Using the molecular invariom approach, the nature of the chemical bonds and charge distribution was investigated; the energy of the Rh-Rh bonds was estimated.

Water-Soluble Bismuth(III) Polynuclear Tyrosinehydroximate Metallamacrocyclic Complex: Structural Parallels to Lanthanide Metallacrowns.

Recently there has been a great deal of interest and associated research into aspects of the coordination chemistry of lanthanides and bismuth-elements that show intriguing common features. This work focuses on the synthesis and characterization of a novel bismuth(III) polynuclear metallamacrocyclic complex derived from aminohydroxamic acid, in order to compare the coordination ability of Bi3+ with the similarly sized La3+ ions. A polynuclear tyrosinehydroximate Bi(OH)[15-MCCu(II)Tyrha-5](NO3)2 (1) was obtained according to the synthetic routes previously described for water-soluble Ln(III)-Cu(II) 15-MC-5 metallacrowns. Correlations between structural parameters of Bi(III) and Ln(III) complexes were analyzed. DFT calculations confirmed the similarity between molecular structures of the model bismuth(III) and lanthanum(III) tyrosinehydroximate 15-metallacrowns-5. Analysis of the electronic structures revealed, however, stronger donor-acceptor interactions between the central ion and the metallamacrocycle in the case of the lanthanum analogue. Thermochromic properties of 1 were studied.

Imine-Based Catechols and o-Benzoquinones: Synthesis, Structure, and Features of Redox Behavior.

Novel sterically hindered catechols of the type 3-(RN=CH)-4,6-DBCatH2 with iminoalkyl or iminoaryl groups in the third position of the aromatic ring have been synthesized and characterized in detail. The o-benzoquinones 3-(RN=CH)-4,6-DBBQ have been synthesized by the oxidation of the corresponding catechols. The oxidation of methylimino-substituted catechol with K3[Fe(CN)6] in alkaline medium leads to the formation of two products: o-quinone and diene-dione, the product of the water addition to the corresponding o-quinone. Some o-benzoquinones react with water or methanol to yield products of water or methanol addition. A prototropic tautomerism is characteristic of catecholaldimines: a quinomethide form is observed in the case of aliphatic amine derivatives, while aryl-substituted catecholaldimines can exist both in the catechol and quinomethide forms in the crystalline state. The formation of dimeric structures motifs is observed in crystals. The electrochemical oxidation of imino-based catechols proceeds via two one-electron processes; the second wave is quasi-reversible, which is unusual for catechols.

Dual Reactivity of 3a,6a-Diaza-1,4-diphosphapentalene: π-Donor versus n-Donor.

Herein, we present the synthesis, single-crystal X-ray structures, and spectroscopic properties for the 1:1 donor-acceptor complexes of 1,2,4,5-tetracyanobenzene (TCNB) with annelated 3a,6a-diaza-1,4-diphosphapentalenes (DDPs) based on cyclohexanone azine (2) and tetralone azine (4). These are the first complexes of an organic π-acceptor with donor phosphorus heterocycles. According to the X-ray study, the DDPs and TCNB molecules are alternately stacked with interplanar distances of 3.335 and 3.404 Å for 2 and 4, respectively, which are suitable for intermolecular π···π interactions. The bond lengths and angles in the component molecules agree with values for neutral species, and the infrared spectra indicate a very slight degree of ionicity. The estimated HOMO-LUMO gap from the onset of optical absorption (1.40 eV) is in agreement with the band gap estimated from the density functional theory calculations for 2 (1.47 eV). By contrast, in a reaction with the related electron acceptor, tetrachloroterephthalonitrile, the DDPs proved to be donors of lone electron pairs in a nucleophilic aromatic substitution reaction of chlorine atoms demonstrating the duality of their electronic nature.

Features of the Molecular Structure and Luminescence of Rare-Earth Metal Complexes with Perfluorinated (Benzothiazolyl)phenolate Ligands.

A set of Sc, Nd, Sm, Eu, Ho, Gd, Er, Yb complexes with perfluorinated 2-(benzothiazol-2-yl)phenolate ligands Ln(SONF)3(DME) were synthesized by the reactions of silylamides Ln[N(SiMe3)2]3 with phenol H(SONF). The structure of the initial phenol, Sc, and Er complexes was established using X-ray analysis, which revealed that the obtained compounds are mononuclear, in contrast to the binuclear non-fluorinated analogues [Ln(SON)3]2 synthesized earlier. All the obtained complexes, both in solid state and in tetrahydrofuran (THF) solutions, upon excitation by light with λex 395 or 405 nm show intense luminance of the ligands at 440-470 nm. The Eu complex also exhibits weak metal-centered emission in the visible region, while the derivatives of Sm luminesces both in the visible and in the infrared region, and Nd, Er, and Yb complexes emit in the near IR (NIR) region of high intensity. DFT (density functional theory) calculation revealed that energy of frontier orbitals of the fluorinated complexes is lower than that of the non-fluorinated counterparts. The level of highest occupied molecular orbital (HOMO) decreases to a greater extent than the lowest occupied molecular orbital (LUMO) level.

Synthesis, structure and long-lived NIR luminescence of lanthanide ate complexes with perfluorinated 2-mercaptobenzothiazole.

To obtain new efficient lanthanide-based NIR luminophores perfluorinated 2-mercaptobenzothiazole was used as a ligand. The ate-complexes [(Ln(mbtF)4)-(Na(DME)3)+] of Nd (1), Sm (2), Tb (3), Er (4), Yb (5) and [(Y(mbtF)4)-(Li(DME)3)+] (6) were synthesized in high yields by the reactions of the respective silylamide compounds Ln[N(SiMe3)2]3 and M[N(SiMe3)2] (M = Li, Na) with 4,5,6,7-tetrafluoro-1,3-benzothiazol-2(3H)-thione (HmbtF) in DME media. The complexes 1-3 and 6 were structurally characterized by X-ray diffraction analysis. It has been shown that the mbtF ligands sensitize the luminescence of Nd, Sm, Tb, Er and Yb ions upon mild UV or blue light excitation. The NIR luminescence of crystalline compounds 1, 2, 4 and 6 has been studied by time-resolved techniques. As expected, the compounds exhibit prolonged NIR luminescence due to the removal of C-H groups from lanthanide centers and the absence of C-O bonds in the coordination sphere of the lanthanides. The synthesized compounds are promising materials for NIR laser applications.

One-Electron Reduction of 2-Mono(2,6-diisopropylphenylimino)acenaphthene-1-one (dpp-mian).

The electrochemical characteristics of 2-mono(2,6-diisopropylphenylimino)acenaphthene-1-one (dpp-mian) have been investigated. One-electron reduction of dpp-mian involves the iminoketone fragment, which is revealed by the EPR spectrum obtained after the electrolysis of the dpp-mian solution in tetrahydrofuran (THF). The reduction of dpp-mian with one equivalent of metallic potassium leads to a similar EPR spectrum. The sodium complex [(dpp-mian)Na(dme)]2 (1) produces an EPR signal with hyperfine coupling on the nitrogen atom of the iminoketone fragment of the dpp-mian ligand. Dpp-mian can also be reduced in a one-electron process by SnCl2 ×(dioxane). In this case, complex (dpp-mian)2 SnCl2 (2) is formed, with the tin atom displaying an oxidation state of +4. Tin(II) chloride dihydrate, SnCl2 ×2(H2 O), also reduces dpp-mian, but the two ligands bound to tin in the product form a new carbon-carbon bond between the ketone moieties of the dpp-mian monoanions to form complex (bis-dpp-mian)HSnCl3 (3). Metallic tin reduces dpp-mian to form the (bis-dpp-mian)2 Sn (4) species. Compounds 1-4 were characterized by X-ray diffraction.

Cerium(iii) complexes with azolyl-substituted thiophenolate ligands: synthesis, structure and red luminescence.

In order to obtain molecular Ce(iii) complexes which emit red light by f-d transitions the azolyl-substituted thiophenolates were used as the ligands. The thiophenolate Ce(iii) complexes were synthesized by the reaction of Ce[N(SiMe3)2]3 with respective thiophenols 2-(2'-mercaptophenyl)benzimidazole (H(NSN)), 2-(2'-mercaptophenyl)benzoxazole (H(OSN)) and 2-(2'-mercaptophenyl)benzothiazole (H(SSN)) in DME media. The structures of the benzimidazolate (Ce(NSN)3(DME)) and benzothiazolate (Ce(SSN)3(DME)) derivatives were determined by X-ray analysis which revealed that the cerium ion in the molecules is coordinated by one DME and three anionic thiophenolate ligands. The lanthanum complex La(OSN)3(DME) has been synthesized similarly and structurally characterized. It was found that the solids of Ce(SSN)3(DME) and Ce(OSN)3(DME) exhibit a broad band photoluminescence peaking at 620 nm which disappears upon solvatation. With an example of OSN derivatives it was proposed that this behaviour is caused by the blue shift of the f-d transition of Ce3+ ions.

Valence-Tautomeric Interconversion in a Bis(dioxolene)cobalt Complex with Iminopyridine Functionalized by a TEMPO Moiety. Phase Transition Coupled with Monocrystal Destruction.

Iminopyridine modified by TEMPO nitroxide was utilized for the synthesis of an octahedral bis(o-semiquinonato)cobalt complex. Variable-temperature magnetic susceptibility measurements detect a valence tautomeric transformation in the temperature range 200-300 K. A reproducible hysteresis loop of about 40 K width is observed on the magnetic moment temperature dependence in the transition region. Differential scanning calorimetry measurements confirm different temperatures of phase transitions accompanying a valence-tautomeric transformation upon heating and cooling. Attempts to study the structural changes associated with the valence-tautomeric transformation by single-crystal X-ray diffraction failed because of the crystal destruction taking place upon cooling from 220 K. The powder X-ray diffraction pattern indicated an essential change of the unit cell upon cooling from 240 K.