Towards molecular alloys: computational and experimental studies on (p-NCC6F4CNSeSeN)x(p-NCC6F4CNSSN)1-x.

The ß-phase of the radical p-NCC6F4CNSSN (1ß) crystallizes in the orthorhombic space group Fdd2 and orders as a canted antiferromagnet with TN = 36 K. Computational studies (B3LYP or M06-2X functional with the cc-pVTZ-PP(-F)+basis set) of the microscopic nearest-neighbour magnetic exchange coupling in 1ß and in the hypothetical isomorphous phase of the selenium radical p-NCC6F4CNSeSeN (2ß) revealed that replacement of S by Se should lead to a significant enhancement in the magnetic ordering temperature by ca. 20% (B3LYP) - 30% (M06-2X). Recrystallization of 2 from solution or via vacuum sublimation afforded only the known diamagnetic, dimeric phase, 2α. Computational studies indicated that both the molecular geometry and charge distribution for 1 and 2 are extremely similar and experimental approaches to form alloys of the general form 11-x2x were explored: attempts to cosublime 1 and 2in vacuo were unsuccessful, forming only 1ß due to the low volatility of 2. Crystallization of pure 1 by solution evaporation was found to afford polymorph 1α (triclinic, P1̄) selectively, irrespective of the solvent employed (CH2Cl2, MeCN, PhMe or THF) but 1α transformed to 1ß upon subsequent vacuum sublimation. Crystallization of 1 in the presence of 2 (up to 20 mol%) from solution evaporation was examined. At 20 mol% there was clear evidence for formation of both 1α and 2α as distinct crystallographic phases by powder X-ray diffraction (PXRD) but some evidence for doping of 2 into 1α at low concentration (≤15 mol percent) was observed. Attempts to sublime a sample of 10.920.1 led to phase separation with the isolation of needle-shaped crystals of pure 1ß characterized by X-ray diffraction.

Synthesis of a Carbene-Stabilized (Diphospha)aminyl Radical and Its One Electron Oxidation and Reduction to Nonclassical Nitrenium and Amide Species.

Herein, we report the synthesis of an acyclic carbene-stabilized diphospha(aminyl) PNP radical CAACMePNPCAACMe 4 (CAACMe = 1-[2,6-bis(isopropyl)phenyl]-3,3,5,5-tetramethyl-2-pyrrolidinylidene) by a facile one-pot, seven-electron reduction of hexachlorophosphazene chloride [Cl3PNPCl3][Cl]. The PNP radical 4 features a conjugated framework with spin density primarily localized on the central nitrogen atom as well as the flanking carbenes. Unlike other tripnictogen radicals, 4 undergoes facile one-electron oxidation and reduction to yield nonclassical nitrenium and amide species [5]+ and [6]-, respectively. The cation [5]+ exhibits conformational flexibility in the solution state between the expected W-shaped geometry [5b]+ and a previously unobserved linear heteroallene-type structure [5a]+, which was characterized in the solid state. The equilibrium was explored both computationally and experimentally, showing that [5a]+ is favored over [5b]+ both enthalpically (ΔH = -2.9 × 103 ± 80 J mol-1) and entropically (ΔS = 4.2 ± 0.25 J mol-1 K-1). The formal amide [6]- displays remarkable flexibility in its coordination chemistry due to the presence of multiple Lewis basic centers, as evidenced by the structure of its potassium complex K262, which exhibits µ, κ-P, κ-P, and η3-PNP coordination modes. Protonation of [6]- leads to the formation of an amine 7, which features a trigonal planar geometry around nitrogen.

Robust S4 ⋠⋠⋠O Supramolecular Synthons: Structures of Radical-Radical Cocrystals [p-XC6 F4 CNSSN]2 [TEMPO] (X=F, Cl, Br, I, CN).

Cocrystallization of the dithiadiazolyl (DTDA) radicals p-XC6 F4 CNSSN (X=F, Cl, Br, I, CN) with TEMPO afforded the 2 : 1 cocrystals [p-XC6 F4 CNSSN]2 [TEMPO] (1-5) whose structures all reflect a common S4 ⋅⋅⋅O supramolecular motif. The nature of this interaction was probed by DFT calculations (M06/aug-cc-pVDZ) on 1 which revealed that the enthalpy of formation of the [C6 F5 CNSSN]2 [TEMPO] supramolecular motif from [C6 F5 CNSSN]2 and TEMPO is substantial (-54.0 kJ mol-1 ). Electronic structure calculations revealed a TEMPO-based doublet S= 1 / 2 configuration as the ground state with limited spin density on the DTDA rings (2.4 %). The corresponding spin quartet state is +78.9 kJ mol-1 higher in energy. An atoms-in-molecules analysis reveals four bond critical points (BCPs) between the TEMPO O and the DTDA S atoms as well as additional BCPs between selected DTDA S atoms and methyl H atoms of the TEMPO molecule. Herein, the structures of 2-5 are considered within the context of a hierarchical view of competing and complementary intermolecular interactions; in particular, the established supramolecular CN⋅⋅⋅S-S synthon is sacrificed in order to form the new S4 ⋅⋅⋅O interaction.

Lewis Acid Assisted Brønsted Acid Catalysed Decarbonylation of Isocyanates: A Combined DFT and Experimental Study.

An efficient and mild reaction protocol for the decarbonylation of isocyanates has been developed using catalytic amounts of Lewis acidic boranes. The electronic nature (electron withdrawing, electron neutral, and electron donating) and the position of the substituents (ortho/meta/para) bound to isocyanate controls the chain length and composition of the products formed in the reaction. Detailed DFT studies were undertaken to account for the formation of the mono/di-carboxamidation products and benzoxazolone compounds.

Structural, Magnetic, and Optical Studies of the Polymorphic 9'-Anthracenyl Dithiadiazolyl Radical.

The fluorescent 9'-anthracenyl-functionalized dithiadiazolyl radical (3) exhibits four structurally determined crystalline phases, all of which are monomeric in the solid state. Polymorph 3α (monoclinic P21/ c, Z' = 2) is isolated when the radical is condensed onto a cold substrate (enthalpically favored polymorph), whereas 3ß (orthorhombic P21 21 21, Z' = 3) is collected on a warm substrate (entropically favored polymorph). The α and ß polymorphs exhibit chemically distinct structures with 3α exhibiting face-to-face π-π interactions between anthracenyl groups, while 3ß exhibits edge-to-face π-π interactions. 3α undergoes an irreversible conversion to 3ß on warming to 120 °C (393 K). The ß-phase undergoes a series of reversible solid-state transformations on cooling; below 300 K a phase transition occurs to form 3γ (monoclinic P21/ c, Z' = 1), and on further cooling below 165 K, a further transition is observed to 3δ (monoclinic P21/ n, Z' = 2). Both 3ß â†’ 3γ and 3γ → 3δ transitions are reversible (single-crystal X-ray diffraction), and the 3γ → 3δ process exhibits thermal hysteresis with a clear feature observed by heat capacity measurements. Heating 3ß above 160 °C generates a fifth polymorph (3ε) which is distinct from 3α-3δ based on powder X-ray diffraction data. The magnetic behavior of both 3α and the 3ß/3γ/3δ system reflect an S = 1/2 paramagnet with weak antiferromagnetic coupling. The reversible 3δ ↔ 3γ phase transition exhibits thermal hysteresis of 20 K. Below 50 K, the value of χm T for 3δ approaches 0 emu·K·mol-1 consistent with formation of a gapped state with an S = 0 ground-state configuration. In solution, both paramagnetic 3 and diamagnetic [3][GaCl4] exhibit similar absorption and emission profiles reflecting similar absorption and emission mechanisms for paramagnetic and diamagnetic forms. Both emit in the deep-blue region of the visible spectrum (λem ∼ 440 nm) upon excitation at 255 nm with quantum yields of 4% (3) and 30% ([3][GaCl4]) affording a switching ratio [ΦF(3+)/ΦF(3)] of 7.5 in quantum efficiency with oxidation state. Solid-state films of both 3 and [3][GaCl4] exhibit emission bands at a longer wavelength (490 nm) attributed to excimer emission.

On the Design of Radical-Radical Cocrystals.

Formation of radical-radical cocrystals is an important step towards the design of organic ferrimagnets. We describe a simple approach to generate radical-radical cocrystals through the identification and implementation of well-defined supramolecular synthons which favor cocrystallization over phase separation. In the current paper we implement the structure-directing interactions of the E-E bond (E=S, Se) of dithiadiazolyl (DTDA) and diselenadiazolyl (DSDA) radicals to form close contacts to electronegative groups. This is exemplified through the preparation and structural characterization of three sets of radical cocrystals; the 2:2 cocrystal [PhCNSSN]2 [MBDTA]2 (4) [MBDTA=methyl benzodithiazolyl] and the 2:1 cocrystals [C6 F5 CNEEN]2 [TEMPO] (E=S, 5; E=Se, 6). In 4 the two types of radical are linked via bifurcated inter-dimer δ+ S⋅⋅⋅Nδ- interactions whereas 5 and 6 exhibit a set of five-centre δ+ E⋅⋅⋅Oδ- contacts (E=S, Se).

Multifunctional Dithiadiazolyl Radicals: Fluorescence, Electroluminescence, and Photoconducting Behavior in Pyren-1'-yl-dithiadiazolyl.

The pyren-1'-yl-functionalized dithiadiazolyl (DTDA) radical, C16H9CNSSN (1), is monomeric in solution and exhibits fluorescence in the deep-blue region of the visible spectrum (440 nm) upon excitation at 241 nm. The salt [1][GaCl4] exhibits similar emission, reflecting the largely spectator nature of the radical in the fluorescence process, although the presence of the radical leads to a modest quenching of emission (ΦF = 98% for 1+ and 50% for 1) through enhancement of non-radiative decay processes. Time-dependent density functional theory studies on 1 coupled with the similar emission profiles of both 1+ and 1 are consistent with the initial excitation being of predominantly pyrene π-π* character. Spectroscopic studies indicate stabilization of the excited state in polar media, with the fluorescence lifetime for 1 (τ = 5 ns) indicative of a short-lived excited state. Comparative studies between the energies of the frontier orbitals of pyren-1'-yl nitronyl nitroxide (2, which is not fluorescent) and 1 reveal that the energy mismatch and poor spatial overlap between the DTDA radical SOMO and the pyrene π manifold in 1 efficiently inhibit the non-radiative electron-electron exchange relaxation pathway previously described for 2. Solid-state films of both 1 and [1][GaCl4] exhibit broad emission bands at 509 and 545 nm, respectively. Incorporation of 1 within a host matrix for OLED fabrication revealed electroluminescence, with CIE coordinates of (0.205, 0.280) corresponding to a sky-blue emission. The brightness of the device reached 1934 cd/m2 at an applied voltage of 16 V. The crystal structure of 1 reveals a distorted π-stacked motif with almost regular distances between the pyrene rings but alternating long-short contacts between DTDA radicals. Solid state measurements on a thin film of 1 reveal emission occurs at shorter wavelengths (375 nm) whereas conductivity measurements on a single crystal of 1 show a photoconducting response at longer wavelength excitation (455 nm).

Studies on a "Disappearing Polymorph": Thermal and Magnetic Characterization of α-p-NCC6F4CNSSN•.

The α-and ß-phases of the thiazyl radical p-NCC6F4CNSSN• (1) can be selectively prepared by careful control of the sublimation conditions, with the α-phase crystallizing preferentially when the substrate temperature is maintained below -10 °C, whereas the ß-phase is isolated when the substrate temperature is maintained at or above ambient temperature. Differential scanning calorimatry studies reveal that the α-phase converts to the ß-phase upon warming over the range 111-117 °C (ΔH = +4 kJ·mol-1) via a melt-recrystallization process, with the ß-phase itself melting at 167-170 °C (ΔHfus = 27 kJ·mol-1). IR and Raman spectroscopy can be used to clearly discriminate between 1α and 1ß. The α-phase shows a broad maximum in the magnetic susceptibility around 8 K that, coupled with a broad maximum in the heat capacity, is indicative of short-range order. Some field dependence of the susceptibility below 3 K is observed, but the lack of features in the ac susceptibility, M vs H plots, or heat capacity mitigates against long-range order in 1α.

Structural Studies of Perfluoroaryldiselenadiazolyl Radicals: Insights into Dithiadiazolyl Chemistry.

The synthesis and structural characterization of a series of perfluoroaryldiselenadiazolyls [DSeDA; p-XC6F4CNSeSeN (X = F, Cl, Br, CF3, NO2, and CN for 2a-2f, respectively)] are described. Concentration-dependent solution UV/vis measurements on 2a follow the Beer-Lambert law and the transitions assigned through time-dependent density functional theory (TD-DFT) studies, indicating little propensity for dimerization in solution (10-3-10-4 M). Solution electron paramagnetic resonance (EPR) spectra reveal that these radicals exhibit a broad featureless singlet around g = 2.04 but form well-resolved anisotropic EPR spectra in frozen solution, from which spin densities were determined and found to reflect an increase in the spin density at the chalcogen in relation to the corresponding dithiadiazolyl (DTDA) radicals, p-XC6F4CNSSN. The solid-state structures of 2a and 2d-2f all adopt spin-paired cis-cofacial dimers in which the dimers are held together via multicenter π*-π* "pancake bonding" interactions. Conversely, 2b and 2c exhibit an orthogonal mode of association, which is unique to DSeDA chemistry but which also affords a singlet ground state evidenced by SQUID magnetometry. The more sterically demanding diselenadiazolyl radical 2f was also prepared and exhibits a trans-antarafacial dimerization mode. DFT studies [UPBE0-D3 ccPVTZ-PP(-F)++] on the model radical HCNSeSeN confirm that each dimer is a stable energy minimum on the potential energy surface, reproducing well the experimental geometric parameters with relative stability in the order cis-cofacial > orthogonal > trans-antarafacial. Computational studies reflect stronger dimerization for DSeDA radicals in relation to their sulfur analogues, consistent with the experimental observation: While 2a and 2d are isomorphous with their corresponding DTDA radicals, 2b, 2c, and 2e-2g are all dimeric, in contrast to their DTDA analogues, which are monomeric in the solid-state. A study on 2f reveals that significant geometric strain accumulates in order to support the propensity for both cis dimerization and intermolecular CN···Se interactions. Conversely, p-NCC6F4CNSSN likely forfeits dimerization in the analogous packing motif in order to release strain but retains the favorable intermolecular CN···S interactions.

Phosphine control of the oxidative addition chemistry of tetrathiocins to palladium(0): characterization of mono-, di-, and hexanuclear palladium(II) dithiolate complexes.

The outcome of the oxidative addition reactions of bis(4',5'-dimethoxybenzo)-1,2,5,6-tetrathiocin to Pd2dba3 under microwave conditions is sensitive to the nature of the phosphine coreagent; the bidentate phosphines dppm, dppe, and dppf afford the mononuclear dithiolates (dmobdt)Pd(dppm) (4), (dmobdt)Pd(dppe) (2), and (dmobdt)Pd(dppf) (5), whereas more labile monodentate phosphines lead to aggregation; Ph3P afforded the dinuclear dithiolate (dmobdt)2Pd2(PPh3)2 (6), whereas (t)Bu3P generated the phosphine-free hexanuclear edge-capped octahedral complex Pd6(dmobdt)6 (7) [dmobdt = 4,5-dimethoxybenzenedithiolate, (MeO)2C6H2S2(2-)].

A magnetostructural investigation of an abrupt spin transition for 1-phenyl-3-trifluoromethyl-1,4-dihydrobenzo[e][1,2,4]triazin-4-yl.

1-Phenyl-3-trifluoromethyl-1,4-dihydrobenzo[e][1,2,4]triazin-4-yl is the first example of a hydrazyl radical that shows a reversible sharp spin transition fully completed within 5(1) K. The nominally first-order transition takes place at ca. 58(2) K and proceeds via subtle changes of intra- and interstack interactions between two similar structural phases. The low-temperature phase (5-60 K) is diamagnetic and has a singlet ground state (2Jexp = -166.8 cm(-1), gsolid = 2.0042, ρ = 0.2%) stemming from a multicenter two-electron interaction. The high-temperature phase (60-300 K) is paramagnetic as a result of noninteracting S = 1/2 spins arising from weakly bound dimers.

Structural, magnetic, and computational correlations of some imidazolo-fused 1,2,4-benzotriazinyl radicals.

1,3,7,8-Tetraphenyl-4,8-dihydro-1H-imidazolo[4,5g][1,2,4]benzotriazin-4-yl (5), 8-(4-bromophenyl)-1,3,7-triphenyl-4,8-dihydro-1H-imidazolo[4,5g][1,2,4]benzotriazin-4-yl (6), and 8-(4-methoxyphenyl)-1,3,7-triphenyl-4,8-dihydro-1H-imidazolo[4,5g][1,2,4]benzotriazin-4-yl (7) were characterized by using X-ray diffraction crystallography, variable-temperature magnetic susceptibility studies, and DFT calculations. Radicals 5-7 pack in 1 D π stacks made of radical pairs with alternate short and long interplanar distances. The magnetic susceptibility (χ vs. T) of radicals 5 and 6 exhibit broad maxima at (50±2) and (50±4) K, respectively, and are interpreted in terms of an alternating antiferromagnetic Heisenberg linear chain model with average exchange-interaction values of J = -31.3 and -35.4 cm(-1) (gsolid = 2.0030 and 2.0028) and an alternation parameter a = 0.15 and 0.38 for 5 and 6, respectively. However, radical 7 forms 1 D columns of radical pairs with alternating distances; one of the interplanar distances is significantly longer than the other, which decreases the magnetic dimensionality and leads to discrete dimers with a ferromagnetic exchange interaction between the radicals (2J = 23.6 cm(-1) , 2zJ' = -2.8 cm(-1) , gsolid = 2.0028). Magnetic exchange-coupling interactions in 1,2,4-benzotriazinyl radicals are sensitive to the degree of slippage and inter-radical separation, and such subtle changes in structure alter the fine balance between ferro- and antiferromagnetic interactions.

Route to benzo- and pyrido-fused 1,2,4-triazinyl radicals via N'-(het)aryl-N'-[2-nitro(het)aryl]hydrazides.

A two-step route to 1,3-disubstituted benzo- and pyrido-fused 1,2,4-triazinyl radicals is presented. The route involves the N'-(2-nitroarylation) of easily prepared N'-(het)arylhydrazides via nucleophilic aromatic substitution of 1-halo-2-nitroarenes, which in most cases gives N'-(het)aryl-N'-[2-nitro(het)aryl]hydrazides in good yields. Mild reduction of the nitro group followed by an acid-mediated cyclodehydration gives the fused triazines, which upon alkali treatment afford the desired radicals. Fifteen examples of radicals are presented bearing a range of substituents at N-1, C-3, and C-7, including the pyrid-2-yl and 8-aza analogues. This route to the N'-(het)aryl-N'-[2-nitro(het)aryl]hydrazides, which works well with benzo- and picolinohydrazides, required a modification for aceto- and trifluoroacetohydrazides that involved a multistep synthesis of asymmetrically 1,1-diaryl-substituted hydrazines.

Exploring the coordination chemistry of 3,3'-di(picolinamoyl)-2,2'-bipyridine: one ligand, multiple nuclearities.

The syntheses, structures, and magnetic properties of three new coordination complexes, tetranuclear [Zn2L(3)(OAc)(OMe)]2·3MeOH·H2O (3), trinuclear [Ni3(L(3))3]·6H2O (4), and a 1-D chain {[Cu2L(3)(OAc)2]2·H2O}n (6), of a polydentate, doubly deprotonated, 3,3'-disubstituted bipyridine ligand [L(3)](2-) are reported. The X-ray crystal structures demonstrate that the ditopic ligand provides a flexible N3 donor set for transition metal ions where each binding pocket shifts from fac to intermediate fac/mer to the mer isomer affording a Ni3 triangle, a Zn4 tetramer, and a 1-D Cu(II) polymer, respectively. This variation in coordination preference is rationalized with the aim of designing future ligands with controlled coordination modes. Magnetic susceptibility studies on 4 reveal it belongs to the rare family of ferromagnetically coupled [Ni3] clusters. In contrast, magnetic studies of the 1-D chain 6 reveal weak antiferromagnetic interactions due to the poor orbital overlap of the singly occupied Cu(II) d(x(2)-y(2)) orbitals with the one-atom bridge that connects them along the Jahn-Teller distortion axis.

C-H bond activation by radical ion pairs derived from R3P/Al(C6F5)3 frustrated Lewis pairs and N2O.

Al(C6F5)3/R3P [R = tert-butyl (tBu), mesityl (Mes), naphthyl (Nap)] frustrated Lewis pairs react with N2O to form species having the formula R3P(N2O)Al(C6F5)3, which react with additional alane to generate proposed frustrated radical ion pairs formulated as [R3P·][(µ-O·)(Al(C6F5)3)2] that can activate C-H bonds. For R = tBu, C-H activation of a tBu group affords [tBu2PMe(C(CH2)Me)][(µ-OH)(Al(C6F5)3)2]. In the case of R = Mes, the radical cation salt [Mes3P·][(µ-HO)(Al(C6F5)3)2] is isolated, while for R = Nap, the activation of toluene and bromobenzene gives [(Nap)3PCH2Ph][(µ-OH)(Al(C6F5)3)2] and [(Nap)3PC6H4Br][(µ-HO)(Al(C6F5)3)2], respectively.

Non-innocent ligand effects on low-oxidation-state indium complexes.

Attempts to coordinate neutral ligands to low oxidation state indium centers are often hindered by disproportionation pathways that produce elemental indium and higher oxidation state species. In contrast, we find that reactions of the salt, InOTf (OTf=trifluoromethanesulfonate), with α-diimine ligands yielded intensely colored compounds with no evidence of decomposition. X-ray structural analysis of InOTf⋅(Mes) DAB(Me) ((Mes) DAB(Me) =N,N-dimesityl-2,3-dimethyl-diazabutadiene; 1) reveals a discrete molecular compound with a pyramidal coordination environment at the indium center, consistent with the presence of a stereochemically active lone pair of electrons on indium and a neutral diazabutadiene chelate ligand. The use of the less-electron-rich (Mes) DAB(H) ligand ((Mes) DAB(H) =N,N-dimesityl-diazabutadiene) engenders dramatically different reactivity and produces a metallopolymer (InOTf⋅(Mes) DAB(H) )∞ (2) linked via CC and InIn bonds. The difference in reactivity is rationalized by cyclic voltammetry and DFT studies that suggest more facile electron transfer from In(I) to the (Mes) DAB(H) and bis(aryl)acenaphthenequinonediimine (BIAN) ligands. Solution EPR spectroscopy indicates the presence of non-interacting ligand-based radicals in solution, whereas solid-state EPR studies reflect the presence of a thermally accessible spin triplet consistent with reversible CC bond cleavage.

Synthesis and properties of imidazolo-fused benzotriazinyl radicals.

1,3-Diphenylbenzo[e][1,2,4]triazin-7(1H)-one, the oxidation product of 1,3-diphenyl-1,4-dihydro-1,2,4-benzotriazin-4-yl (Blatter's radical), reacts with N'-arylbenzamidines in PhMe at ca. 100 °C in the presence of N,N-diisopropylethylamine (Hünig's base) (1 equiv.) to give N'-aryl-N-(1,7-dihydro-7-oxo-1,3-diphenylbenzo[e][1,2,4]triazin-6-yl)benzimidamides in 49-95% yield. In neat AcOH heated at ca. 120 °C, N'­aryl-N-(1,7-dihydro-7-oxo-1,3-diphenylbenzo[e][1,2,4]triazin-6-yl)benzimidamides cyclodehydrate to give the novel 8-substituted 1,3,7-triphenyl-4,8-dihydro-1H-imidazo[4,5-g][1,2,4]benzotriazin-4-yls in 13-81% yield. During the optimization of this cyclodehydration an additional oxazole fused benzotriazinyl radical 1,3,7-triphenyl-1,4-dihydro[1,3]oxazolo[4,5-g][1,2,4]benzotriazin-4-yl was isolated as a side product and characterized. The CV and EPR data of the imidazolo- and oxazolo-fused radicals are presented as well as single crystal X-ray structures of 1,3,7-triphenyl-1,4-dihydro-[1,3]oxazolo[4,5-g][1,2,4]benzotriazin-4-yl and 1,3,7,8-tetraphenyl-4,8-dihydro-1H-imidazo[4,5-g][1,2,4]benzotriazin-4-yl.

Lanthanide complexes facilitate wound healing by promoting fibroblast viability, migration and M2 macrophage polarization.

A tridentate ligand LH3 ((2-hydroxy-3-methoxybenzylidene)-2-(hydroxyimino)propanehydrazide) comprising o-vanillin, hydrazone and oxime donor groups has been employed to prepare a series of tetranuclear Ln(III) complexes. The reaction of ligand LH3 with Ln(NO3)3 [Ln = Sm, Eu, Gd, Tb, Dy, Ho, Er] in MeOH yielded Ln4(LH)6(MeOH)2 (Ln = Sm(1), Eu(2), Gd(3), Tb(4), Ho (6) and Er (7))] whereas the corresponding reaction with Dy(NO3)3 afforded Dy4(LH)4(LH2)2(OH)2 (5). All complexes were characterized by various analytical techniques including single crystal X-ray diffraction, IR spectroscopy, UV-Vis spectroscopy, and elemental analysis. To investigate the potential of these lanthanide complexes for wound healing applications, their effects on fibroblast viability, migration, and M2 macrophage polarization were evaluated. The cytotoxicity assessment revealed that complexes 2(Eu), 4(Tb), 5(Dy), and 7(Er) significantly enhanced fibroblast viability compared to the negative control (NC). In vitro wound healing assay demonstrated that complexes 2(Eu) and 7(Eu) substantially promoted fibroblast migration compared to the NC. Moreover, complex 2(Eu) exhibited significant anti-inflammatory effects by reducing the phagocytic ability of lipopolysaccharide (LPS)-stimulated macrophage cells and attenuating nitric oxide (NO) production. In conclusion, among the series of complexes tested, complex 2(Eu) displayed the most potent anti-inflammatory effect on macrophage cells, while simultaneously promoting fibroblast viability and migration. This unique combination of properties renders complex 2 (Eu) highly promising for wound healing applications.

Ferromagnetic interactions in a 1D alternating linear chain of π-stacked 1,3-diphenyl-7-(thien-2-yl)-1,4-dihydro-1,2,4-benzotriazin-4-yl radicals.

X-ray studies show that 1,3-diphenyl-7-(thien-2-yl)-1,4-dihydro-1,2,4-benzotriazin-4-yl (6) adopts a distorted, slipped π-stacked structure of centrosymmetric dimers with alternate short and long interplanar distances (3.48 and 3.52 Å). Cyclic voltammograms of 7-(thien-2-yl)benzotriazin-4-yl 6 show two fully reversible waves that correspond to the -1/0 and 0/+1 processes. EPR and DFT studies on radical 6 indicate that the spin density is mainly delocalized over the triazinyl fragment. Magnetic susceptibility measurements show that radical 6 obeys Curie-Weiss behavior in the 5-300 K region with C=0.378 emu K mol(-1) and θ=+4.72 K, which is consistent with ferromagnetic interactions between S=1/2 radicals. Fitting the magnetic susceptibility revealed the behavior is consistent with an alternating ferromagnetic chain (g=2.0071, J(1) =+7.12 cm(-1), J(2) =+1.28 cm(-1)).

Antiferromagnetic interactions in 1D Heisenberg linear chains of 7-(4-fluorophenyl) and 7-phenyl-substituted 1,3-diphenyl-1,4-dihydro-1,2,4-benzotriazin-4-yl radicals.

7-(4-Fluorophenyl) and 7-phenyl-substituted 1,3-diphenyl-1,4-dihydro-1,2,4-benzotriazin-4-yl radicals were characterized by X-ray diffraction analysis and variable-temperature magnetic susceptibility studies. The radicals pack in 1D π stacks of equally spaced slipped radicals with interplanar distances of 3.59 and 3.67 Å and longitudinal angles of 40.97 and 43.47°, respectively. Magnetic-susceptibility studies showed that both radicals exhibit antiferromagnetic interactions. Fitting the magnetic data revealed that the behavior is consistent with 1D regular linear antiferromagnetic chain with J=-12.9 cm(-1), zJ'=-0.4 cm(-1), g=2.0069 and J=-11.8 cm(-1), zJ'=-6.5 cm(-1), g=2.0071, respectively. Magnetic-exchange interactions in benzotriazinyl radicals are sensitive to the degree of slippage, and inter-radical separation and subtle changes in structure alter the fine balance between ferro- and antiferromagnetic interactions.