Athanassios K. Boudalis

University of Strasbourg | UNISTRA · Institut de Chimie de Strasbourg UMR 7177

3,3',3''-(Benzene-1,3,5-triyl)tris(1-phenyl-1H-benzo[e][1,2,4]triazin-4-yl) (1) is a C3-symmetrical triradical comprised of three Blatter radical units connected at the 1, 3, 5 positions of a central trimethylenebenzene core. This triradical has an excellent air, moisture, and thermal stability. Single-crystal XRD indicates that triradical 1 adopts...

A mixed-ligand phthalocyanine/porphyrin yttrium(III) radical double-decker complex (DD) was synthesized using the custom-made 5,10,15-tris(4-methoxyphenyl)-20-(4-((trimethylsilyl)ethynyl)phenyl)porphyrin. The trimethylsilyl functionality was then used to couple two such complexes into biradicals through rigid tethers. Glaser coupling was used to sy...

The Cover Feature illustrates the perspective of using magnetic ionic liquids as single‐component magnetocaloric thermal greases, combining magnetic cooling and high thermal contact with the heat exchange surfaces. Such a homogeneous material would obviate the need of mixing solid magnetocaloric materials with thermal greases to achieve the same ef...

[Gd 5 (L) 16 (H 2 O) 8 ](Tf 2 N) 15 was obtained from reaction of Gd 2 O 3 with 1‐carboxymethyl‐3‐ethylimidazolium chloride (LHCl). The material was found to be an ionic liquid that freezes to glassy state on cooling to ‐30°C. Variable‐temperature magnetic studies reveal the presence of weak magnetic intramolecular interactions in the glass. Isothe...

FID-detected nutations of the antiferromagnetic crystal form of [Y(pc)2]• demonstrated that its radical spin can be coherently driven in the its magnetically condensed undeuterated phase and at room temperature. Liquid-helium...

A dimeric Cu(II) complex [Cu(II)2L2(μ2-Cl)Cl] (1) built from an asymmetric tridentate ligand (2-(((2-aminocyclohexyl)imino)methyl)-4,6-di-tert-butylphenol) and weakly coordinating anions has been synthesized and structurally characterized. In dichloromethane solution, 1 exists in a monomeric [Cu(II)LCl] (1') (85%)-dimeric (1) (15%) equilibrium, and...

We built a broadband Electron Paramagnetic Resonance (EPR) spectrometer capable of field- and frequency sweep experiments under field-, microwave amplitude- and microwave frequency-modulation detection modes (HM, AM, and FM, respectively). The spectrometer is based on a coplanar waveguide (CPW) architecture, with the sample being deposited on top o...

A 16-line pattern has been theoretically predicted, but hitherto not reported, for the Electron Paramagnetic Resonance (EPR) spectrum of antiferromagnetically coupled CuII triangles experiencing isotropic exchange of isosceles magnetic symmetry. Now, the crystallization of such a triangular species and its X-ray structure determination in a polar s...

Triangular complexes of half‐integer spins, spin triangles, are the oldest molecular nanomagnets, the magnetic properties of them have been studied long before molecular magnetism was delineated as a research field. Read more about the history of their study chemical diversity together with recent developments in terms of theoretical ideas and new...

Magnetic coordination complexes are described as ready-to-go active quantum components in spintronic solid state device architectures. Demonstration of quantum behavior of Fe(II) spin crossover complexes and of Lanthanide (III) single molecule magnets in molecular spin valves, transistors, and resonators as well as the implementation of Grover's se...

Spin triangles, i.e. triangular complexes of half-integer spins, are the oldest Molecular Nanomagnets (MNMs). Their magnetic properties have been studied long before Molecular Magnetism was delineated as a research field. This Review presents the history of their study, with references to the parallel development of new experimental investigations...

Single‐crystal electron paramagnetic resonance studies of a ferromagnetic copper(II) triangle were combined with ab initio calculations, and analyzed through a detailed multispin Hamiltonian to explain the origins of the ground state ferromagnetism and anisotropy. This combined analysis demonstrated that the symmetry of the magnetic orbitals is res...

Two anionic complexes, {[Cu3(µ3-OH)(µ-4-Ph-pz)3Cl3]2[Cu(4-Ph-pzH)4](µ-Cl)2}2− (1) and [Cu3(µ3-OH)(µ-pz)3(µ1,1-N3)2(N3)]− (2), crystallize as one-dimensional polymers, held together by weak Cu-(µ-Cl) and Cu-(µ-N3) interactions, respectively. Variable temperature magnetic susceptibility analyses determined the dominant antiferromagnetic intra-Cu3 exc...

Ac susceptometry and magnetic hysteresis studies are the two most used techniques for the basic characterization of magnetic relaxation properties of Single-Molecule Magnets. Nevertheless, the full quantitative treatment of such studies is rarely carried out, in particular as regards the absolute magnitudes of the in-phase (χʹ) and out-of-phase (χʺ...

Previously reported ferromagnetic triangles (NnBu4 )2 [Cu3 (μ3 -Cl)2 (μ-4-NO2 -pz)3 Cl3 ] (1), (PPN)2 [Cu3 (μ3 -Cl)2 (μ-pz)3 Cl3 ] (2), (bmim)2 [Cu3 (μ3 -Cl)2 (μ-pz)3 Cl3 ] (3) and newly reported (PPh4 )2 [Cu3 (μ3 -Cl)2 (μ-4-Ph-pz)3 Cl3 ] (4) were studied by magnetic susceptometry, electron paramagnetic resonance (EPR) spectroscopy and ab initio ca...

The magnetizations of magnetic molecules are aligned to magnetic fields like a sailor's compass. It is now shown that some such molecules are actually magnetoelectric, and that their magnetizations can also be controlled by external electric fields. See Boudalis and co-workers, DOI: 10.1021/jacs.9b09101.

Mononuclear chromium(III) complexes of formula mer-[CrIIICl3(pz*H)3] (pz*H = pyrazole (pzH), and substituted pyrazoles: 3-Me-pzH, 4-Me-pzH, 4-Cl-pzH, 4-Br-pzH, 4-I-pzH) and trans-[CrIIICl2(pzH)4]Cl were synthesized from reactions of CrCl3 hydrate and pyrazole ligands and crystallographically characterized. The fluxional behavior of the complexes, a...

Two molecular spin qubits are studied with pulsed electron paramagnetic resonance (EPR) spectroscopy under electric fields to assess their magnetoelectric (ME) couplings and electric spin control. [Fe3O(PhCOO)6(py)3]ClO4·py (Fe 3 ) is characterized by strong Dzyaloshinskii-Moriya interactions (DMI) which induce important magnetoanisotropy, whereas...

The structurally related spin triangles [Fe3O(PhCOO)6(py)3]ClO4·py (Fe3) and [Cr3O(PhCOO)6(py)3]ClO4·0.5py (Cr3) were studied as frozen py-d5 solutions with various pulsed Electron Paramagnetic Resonance (EPR) spectroscopy experiments, and under identical experimental conditions. Field-swept Hahn echo experiments revealed a match with continuous-wa...

Two trinuclear CuII pyrazolato complexes with a Cu3(μ3-E)-core (E = O2- or OH-) and terminal nitrite ligands in two coordination modes were characterized crystallographically, spectroscopically, and electrochemically. One-electron oxidation of the μ3-O species produces a delocalized, mixed-valent, formally CuII2CuIII-nitrite, but no nitrate. In con...

RÉSUMÉ Les propriétés magnétiques des matériaux sont exploitées dans de nombreuses applications : des plus classiques, composants électromécaniques, enregistrement magnétique, aux plus élaborées et futuristes, comme la réfrigération magnétique ou l'électronique de spin. Cet article introduit a notion de Liquide Ionique (LI) avec son extension aux c...

The spin of a polynuclear Molecular Nanomagnet can couple to externally applied electric fields, as evidenced by Electron Paramagnetic Resonance experiments. This is the first demonstration of magnetoelectric coupling in this class of magnetic materials and was observed for the spin‐chiral antiferromagnetic triangle [Fe3O(O2CPh)6(py)3]ClO4⋅py. This...

Single‐crystal EPR experiments show that the highly symmetric antiferromagnetic half‐integer spin triangle [Fe3O(O2CPh)6(py)3](ClO4)*py (1) possesses a ST = 1/2 ground state exhibiting high g‐anisotropy due to antisymmetric exchange (Dzyaloshinskii‐Moriya) interactions. EPR experiments under static electric fields parallel to the triangle's plane (...

The X-ray crystal structure of the Cu II complex [Cu 3 (µ 3 -OH)(µ-pz) 3 (PhCOO) 3 ] ⁻ (pz ⁻ = pyrazolato anion) shows an isosceles triangular core, further forming a hexanuclear H-bonded aggregate. Cleavage of the H-bonds in solution...

The synthesis and characterization of a preparation of the [Fe{(SePPh2)2N}2] complex (1) is described. X-ray crystallography shows that this system contains a tetrahedral FeSe4 coordination sphere. The structural features of 1 are compared with those of similar first row transition element complexes, including a recently reported preparation of [Fe...

The reaction of mixtures of Fe(O2CMe)2∙2H2O and Ni(O2CMe)2∙4H2O of various compositions with di-2-pyridyl ketone (py2CO, dpk) in MeCN under an inert atmosphere afforded a family of hetero-metallic enneanuclear clusters with general formula [Fe9-xNix(µ4-OH)2(O2CMe)8(py2CO2)4] (2, x =1.00; 3: x = 6.02; 4, x = 7.46; 5, x = 7.81). Clusters 2 - 5 are is...

Complexes (bmim)2[Cu3(μ3-Cl)2(μ-pz)3Cl3] (1), (bmim)[Cu3(μ3-OH)(μ-pz)3Cl3] (2) and (bmim)2[Cu3(μ3-OH)(μ-Cl)(μ-pz)3Cl3] (3) were synthesized (bmim⁺ = 1-butyl-3-methylimidazolium). Dianionic complexes 1 and 3 were obtained as crystalline solids, whereas the monoanionic complex 2 was obtained as a viscous paste. Magnetic susceptibility and X-band EPR...

Complex [Fe3O(O2CPh)6(py)3]ClO4·py (1) crystallizes in the hexagonal P63/m space group, and its cation exhibits a crystallographically imposed D3h symmetry due to a C3 axis passing through the oxide of its {Fe3O}(7+) core. Single-crystal unit-cell studies carried out with synchrotron radiation confirmed that this symmetry is retained down to 4.5 K;...

In order to examine the possibility of using yttrium(III) in the crystal engineering of hydrogen-bonded coordination complexes and to compare the molecular and supramolecular YIII/Cl- or NCh 3-/DMU chemistry with the already well-developed Ln III/Cl- or NO3-/DMU chemistry (LnIII = lanthanide, DMU = N,N′-dimethylurea), compounds [Y(DMU)6][YCl6] (1)...

Eight novel Fe-6(III) clusters with the amino-alcohol ligands 3-amino-1-propanol (apH), N-hydroxyethylpiperidine (N-hepipH), 2-hydroxyethylpiperidine (2-hepipH), 2-aminobenzylalcohol (2-abzaH), N-hydrox-yethylmorpholine (N-hemorH) and ethanolamine (eaH), [Fe6O2(OH)(2)L-2((CH3)(3)CCO2)(10)] (LH = apH, 1; N-hepipH, 2; 2-hepipH, 3; 2-abzaH, 4), [Fe6O2...

The 1D coordination polymer [MnIII6O2(O2CC6H4CO2)(salox)6(dmf)4]n·2n(dmf) (2·2n(dmf)) was obtained from the reaction of [MnIII6O2(O2CPh)2(salox)6(Me2CO)2(H2O)2]·2Me2CO (1·2Me2CO) with excess of terephthalic acid in MeCN/dmf. The structure of 2 consists of [MnIII6O2(salox)6(dmf)4]2+ units bridged through the terephthalato dianions. The Mn6 units pre...

A new end-to-end azide-bridged one-dimensional coordination polymer, [MnIII(L)(μ1,3–N3)] n (1) (where L represents the dianionic form of the neutral tetradentate Schiff base H2L obtained by 1 : 2 condensation of ethane-1,2-diamine, and 5-chloro-2-hydroxyacetophenone in methanol), has been synthesized and characterized by elemental analyses, IR spec...

Nucleophilic attack by the carbanion −CH2COCH3 at the carbonyl carbon atoms of 2,6-di-(2-pyridylcarbonyl)pyridine, pyCOpyCOpy, in the presence of Mnn+ ions under basic conditions has yielded the cationic cluster [Mn4(OH)2(L)2(H2O)2](ClO4)4 (1), where L2− is the (py)C(CH2COCH3)(O−)(py)C(CH2COCH3)(O−)(py) dianion. The cluster cation possesses a plana...

Five novel pentanuclear Fe(3+) clusters with the aliphatic amino-alcohol ligands 3-amino-1-propanol (Hap) and 2-(hydroxymethyl)piperidine (Hhmpip) [Fe(5)(μ(3)-Ο)(2)(L)(4)(O(2)CR)(7)] [L = ap(-), R = Ph (1); L = ap(-), R = C(CH(3))(3) (2); L = hmpip(-), R = Ph (3); L = hmpip(-), R = C(CH(3))(3) (4)] and [Fe(5)(μ(4)-Ο)(μ(3)-Ο)(O(2)CC(CH(3))(3))(8)(ap...

The combined use of di-2-pyridyl ketone [(py)2CO] and azides (N3−) in nickel(II) and cobalt(II) pivalate chemistry has afforded complexes [Ni9(N3)2(O2CCMe3)8{(py)2CO2}4] (1) and [Co9(N3)2(O2CCMe3)8{(py)2CO2}4] (2), where (py)2CO22− is the gem-diolate(−2) form of (py)2CO. The complexes are isostructural and crystallize in the monoclinic P21/c space...

Complex [Fe(II)Gd(III){pyCO(OEt)pyCOH(OEt)py}(3)](ClO(4))(2) (1) crystallizes in the Cc space group and contains one hexacoordinate ferrous ion and one enneacoordinate Gd(III) ion. Complex [Fe(2)(II)Gd(III){pyCO(OEt)py}(4)(NO(3))(H(2)O)][Gd(NO(3))(5)](0.5)(ClO(4)) (2) crystallizes in the C2/c space group and contains two hexacoordinate ferrous ions...

The magnetic properties of the antiferromagnetic basic iron(III) carboxylate [Fe(3)O(O(2)CPh)(6)(H(2)O)(3)]ClO(4)·py are studied by magnetic susceptometry and electron paramagnetic resonance spectrocopy. Ac susceptometry under moderate external magnetic fields reveals magnetic relaxation at liquid helium temperatures.

The synthesis and properties are reported of a new Fe(7) cluster obtained from the reaction of ferrocene-1,1'-dicarboxylic acid (fdcH(2)) with FeCl(2)·4H(2)O in MeOH under ambient light conditions. The compound is the mixed-anion salt [Fe(7)O(3)(OMe)(fdc)(6)(MeOH)(3)][FeCl(4)]Cl(2) (1; 8Fe(III)), containing six (fdc(n-)) groups as peripheral ligand...

The combination of terepthaloylbisglycinate (TBG2−) and metal ions at room temperature results in the formation of five coordination polymers formulated as [M(μ-TBG)(μ-H2O)(H2O)2]·2H2O, where M = Co (1) and Cu (2), [Mn(μ-TBG)(H2O)4]·2H2O (3), [Cd(μ-TBG)(H2O)3]·2H2O (4) and [Pb(μ-TBG)(H2O)2]·3H2O (5). The dimensionality of the final product is affec...

The reactions of salicylaldehyde oxime (H2salox) with CuII precursors yielded the known complexes [Cu(Hsalox)2] (1) and [Cu(Hsalox)2]n (2), as well as complexes [Cu3(salox)(L1)(L2)]·MeCN (3·MeCN), [CuCl(L1)] (4) and [Cu2Na(O2CMe)5(HO2CMe)]n (5), where L1−=o-O–C6H4–CHNO–C(CH3)NH and L23−=o-O–C6H4–CHNO–C(o-O–C6H4)N. L1− was formed in situ via the nuc...

A series of lanthanide(III) coordination polymers [{La(Ben)3(H2O)2} 3 (4,40-BPNO)0.5 3 HBen 3DMF]n (1), [{Ce- (Ben)3(4,40-BPNO)(H2O)2} 3DMF]n (2), [Tb(Ben)3(4,40-BPNO)0.5(H2O)]n (3), [{Ln(Ben)3(4,40-BPNO)(H2O)2} 3 HBen]n [Ln = La (4), Eu (5), Gd (6), Tb (7)] are synthesized and structurally characterized (where Ben=benzoate; HBen=benzoic acid; 4,40...

The reaction of ethylene diamine with Cu(NO3)2�3H2O and an excess of NaN3 (1:2:4 molar ratio) lead to the formation of copper-azido based polymer [Cu4(N3)8(en)2]n (1), which has been successfully characterized by elemental analyses, IR spectroscopy, single-crystal X-ray diffraction and variable temperature magnetic study. X-ray crystal structure de...

One-dimensional coordination polymer {[1H,9H-ade]2[MnL2]∙4H2O}n (1) and {[1H,3H-cyt]2[CuL2]∙6H2O}n (2) (ade=adenine, cyt=cytosine, L=dianion of 2,3-pyridinedicarboxylic acid) are selectively synthesized and variable-temperature magnetic susceptibility measurements revealed weak antiferromagnetic interactions within the chains of 1 and 2 (J=−0.29cm−...

Two series of basic iron(III) carboxylates [Fe3O(O2CR)6(H2O)3]A were prepared, with R = CCl3, CHBr2, CH2F, CH2Cl, C(OH)Ph2, H, Ph, (CH2)3Cl, Me, CHMe2, Et, CMe3. For the former series (1–12) A −  = ClO4-_{4}^{\,\,-} and for the latter (13–24) A −  = NO3-_{3}^{\,\,-}. Complexes with R = CF3 were inaccessible for either counteranion, with all synthet...

The complexes [Cu2(o-NO2-C6H4COO)4(PNO)2] (1), [Cu2(C6H5COO)4(2,2'-BPNO)] n (2), [Cu2(C6H5COO)4(4,4'-BPNO)] n (3), [Cu(p-OH-C6H4COO)2(4,4'-BPNO)2·H2O] n (4), (where PNO = pyridine N-oxide, 2,2'-BPNO = 2,2'-bipyridyl-N,N'-dioxide, 4,4'-BPNO = 4,4'-bipyridyl-N,N'-dioxide) are prepared and characterized and their magnetic properties are studied as...

Complexes [M(II)Gd(III){pyCO(OEt)pyC(OH)(OEt)py}₃](ClO₄)₂·EtOH [M(II) = Cu(II) (1), Mn(II) (2), Ni(II) (3), Co(II) (4) and Zn(II) (5)] crystallize in the monoclinic Cc space group and contain one hexacoordinate M(II) ion and one enneacoordinate Gd(III) ion, bridged by three {pyCO(OEt)pyC(OH)(OEt)py}⁻ ligands. Magnetic susceptibility measurements in...

Complexes [MIIGdIII{pyCO(OEt)pyC(OH)(OEt)py}3](ClO4)2·EtOH [MII = CuII (1), MnII (2), NiII (3), CoII (4) and ZnII (5)] crystallize in the monoclinic Cc space group and contain one hexacoordinate MII ion and one enneacoordinate GdIII ion, bridged by three {pyCO(OEt)pyC(OH)(OEt)py}− ligands. Magnetic susceptibility measurements indicate a ferromagnet...

Complex [Fe2{pyCO(OMe)pyCO(OMe)py}2(MeO)2](ClO4)2·MeOH (1·MeOH) is prepared by reaction of iron(III) perchlorate and dpcp in MeOH at ambient temperature. It crystallizes in the triclinic P1¯ space group and it consists of two centrosymmetric dinuclear crystallographically independent molecules. The dpcp ligand is in its bis-hemiacetal form; both it...

A systematic investigation of the 1:2:1:2 Cu(NO3)·2.5H2O/H2L/bpy/LiOH·H2O (H2L = maleamic acid) reaction system in MeCN/H2O was carried out. The compounds [Cu2(HL)2(bpy)2(H2O)2](NO3)2 (1), [Cu2(HL)2(bpy)2(H2O)2](NO3)2·2H2O (1·2H2O), [Cu2Li2(L′)2(bpy)2(H2O)6][Cu2(HL)2(bpy)2(H2O)2](NO3)4 (2), [Cu4(L′)2(NO3)2(bpy)4(H2O)2](NO3)2·2H2O (3·2H2O) and [Cu(L...

The use of 2-pyridyl ketone oximes, pyC(R)NOH (R=H, Me), in iron(III) carboxylate chemistry yielded the tetranuclear complexes [Fe4O2Cl2(O2CPh)2{pyC(R)NO}4] (R=H, 1; R=Me, 2). The crystal structure of 2 revealed the presence of a central [Fe4(μ3-O)2]8+ core comprising four FeIII ions in a ‘butterfly’ disposition and two μ3-O2− ions, each bridging t...

Compound [Cu(3)(N(3))(6)(DMF)(2)](n) () was initially obtained in a serendipitous way during efforts to prepare a Cu(II)/N(3)(-)/Mebta coordination polymer (Mebta = 1-methylbenzotriazole). With the identity of established by single-crystal crystallography, a rational preparative route to this complex was designed and carried out by reacting Cu(ClO(...

The use of 1,1'-carbonyldiimidazole, (im)(2)CO, for the synthesis of imidazolate (im(-)) and/or imidazole (Him)-containing copper(II) coordination polymers is described. The [Cu(2)(O(2)CMe)(4)(H(2)O)(2)]/(im)(2)CO reaction system in EtOH yields the new polymeric species [Cu(O(2)CMe)(im)(Him)(EtOH)](n) () and the known compound [Cu(im)(2)](n) (), de...

Reaction of copper(ll) perchlorate with di-2,6-(2-pyridylcarbonyl)pyridine (pyCOpyCOpy, dpcp) in the presence of sodium azide yields complex [Cu 4(N3)2{pyC(OMe)(0)pyC(OMe)(0)py}2(MeOH)2](CI0 4) .2MeOH (1 .2MeOH), which crystallizes in the monoclinic P2 1/c space group. Similar reaction of cobalt(ll) nitrate yields complex [Co 4(N 3) 2(N0 3) 2{pyC(O...

The use of 1,1′-oxalyldiimidazole, (im)COCO(im), for the synthesis of coordination complexes is explored for the first time. The [Cu2(O2CMe)4(H2O)2]/(im)COCO(im) reaction system in 96% EtOH yields the new, 1D coordination polymer [Cu(ox)(Him)2]n (1), where Him is the neutral imidazole and ox2− is the oxalate(-2) ligand. A mechanism for the hydrolyt...

The simultaneous presence of benzilic acid [Ph2C(OH)CO2H] and tptz [2,4,6-tri(2-pyridyl)-1,3,5-triazine] in FeIII-containing reaction mixtures leads to partial and/or quantitative metal reduction. In the presence of the oxidative NO3– ions in the reaction mixture, partial reduction of the metal leads to the isolation of a heptacoordinate FeII–nitra...

The use of salicylaldehyde oxime (H2salox) in manganese(III) carboxylate chemistry has yielded new members of the family of hexanuclear compounds presenting the [Mn6(μ3-O)2(μ2-OR)2]12+ core, complexes [MnIII6(μ3-O)2(O2CPh)2(salox)6(L1)2(L2)2] (L1=py, L2=H2O (1); L1=Me2CO, L2=H2O (2); L1=L2=MeOH (3)). Addition of NaOMe to the acetonitrile reaction m...

Complex [Ni 5{pyCOpyC(O)(OMe)py} 2(O 2CMe) 4(N 3) 4(MeOH) 2].2MeOH.2.6H 2O ( 1.2MeOH.2.6H 2O) was synthesized by the reaction of Ni(O 2CMe) 2.4H 2O with pyCOpyCOpy and NaN 3 in refluxing MeOH. It crystallizes in the monoclinic C2/ c space group and consists of five Ni (II) atoms in a helical arrangement. Direct current magnetic susceptibility studi...

Complexes [Fe(Hhbi)(2)(NO(3))].2EtOH (1.2EtOH) and [Fe(2)(mu-OH)(2)(Hhbi)(4)].2H(2)O.8EtOH (2.2H(2)O.8EtOH) crystallize in the orthorhombic Fdd2 and P4(2)2(1)2 space groups, respectively (Hhbi(-) = the monoanion of 2-(2'-hydroxyphenyl benzimidazole). Complex 1 exhibits paramagnetic relaxation as evidenced by Mossbauer spectroscopy, and significant...

The preparation and crystal structures of two linear chain compounds of oxo-centered triangular Mn clusters are reported. {[Mn4O(O2CMe)8(py)]·2MeCN}∞ (1·2MeCN)∞ was formed when a concentrated solution of [Mn3O(O2CMe)6(py)3]·py in MeCN was left undisturbed at room temperature for several weeks. The repeating unit of the chain polymer (1·2MeCN)∞ cons...

Metal-assisted solvolysis of di-2,6-(2-pyridylcarbonyl)pyridine (pyCOpyCOpy, dpcp) by M(O2CMe)2·xH2O (MII = CuII, CoII) led to complex [Cu4{pyC(O)2pyC(O)(OEt)py}(O2CMe)5(EtOH)2] (1), when the reaction was carried out in EtOH, and to complex [Co4{pyC(O)(OMe)pyC(O)(OMe)py}2(O2CMe)2(N3)2] (2), when the reaction was carried out in MeOH in the presence...

The systematic investigation of the parameter space of the CuCl2/H2mal/phen reaction system in MeOH resulted in the isolation of seven different complexes either as mixtures or in pure form, six of which have been structurally characterized. The molar ratios of the reactants and the crystallization methods have been systematically varied, leading t...

Room-temperature aerobic reaction of [Fe(MeCN)4][ClO4]2 with 1,3-bis(2-pyridinecarboxamido)propane (H2bpp) yields the tetrairon(III) complex [Fe4(H2bpp)4(μ-OH)2(μ-OHO)][ClO4]7·2H2O·xMeCN (1·xMeCN, 0 ≤ x ≤ 3). Crystal structure determination reveals that 1·3MeCN is a new member of the tetrairon(III) family, bridged solely by two hydroxido ligands an...

Complexes [Fe9(X)2-(O2CMe)8{(2-py)2CO2}4] (X(-)=OH(-) (1), N3(-) (2), and NCO(-) (3)) have been prepared by a route previously employed for the synthesis of analogous Co(9) and Ni(9) complexes, involving hydroxide substitution by pseudohalides (N3(-), NCO(-)). As indicated by DC magnetic susceptibility measurements, this substitution induced higher...

The ligand, 2-((2-hydroxy-5-methyl-3-((pyridin-2-ylmethylamino)methyl) benzyl)(2-hydroxybenzyl)amino)acetic acid (H3HPBA), which contains a donor atom set that mimics that of the active site of purple acid phosphatase is described. Reaction of H3HPBA with iron(iii) or iron(ii) salts results in formation of the tetranuclear complex, [Fe4(HPBA) 2(OAc...

Aerobic reactions of Co(O2CR)2 with 2-(hydroxymethyl)pyridine (hmpH), in the presence of ClO4– counterions give the hexanuclear, mixed-valence clusters [CoII4CoIII2(O2CR)4(hmp)8](ClO4)2 [R = Me (1), Ph (2)] which possess the unprecedented [CoII4CoIII2(μ3-OR′)4(μ-OR′)4]6+ [R′ = (2-pyridyl)CH2-] core. Replacement of ClO4– by N3– in the reaction mixtu...

Reaction of [Cu2(O2CMe)4(H2O)2] with 2,6-di-(2-pyridylcarbonyl)-pyridine (pyCOpyCOpy or dpcp) in MeCN-H2O 10:1, led to the pentanuclear copper(II) complex [Cu5(O2CMe)6{pyC(O)(OH)pyC(O)(OH)py}2] () which crystallizes in the triclinic P1 space group. The copper(II) atoms are arranged in an "S"-shaped configuration, and are bridged by the doubly depro...

Doubly bridged mu-alkoxo-mu-X (X = pyrazolato or acetato) dinuclear MnIII complexes of 2-hydroxy-N-{2-hydroxy-3-[(2-hydroxybenzoyl)amino]propyl}benzamide) (H5L1) and 2-hydroxy-N-{2-hydroxy-4-[(2-hydroxybenzoyl)amino]butyl}benzamide (H5L2), [Mn2(L)(pz)(MeOH)4].xMeOH (1, L = L1, x = 0.5; 2, L = L2, x = 0; Hpz = pyrazole) and [Mn2(L1)(OAc)(MeOH)4] (3)...

In an effort to better understand the nature of the species which may be involved in the selective extraction of actinides over the lanthanides – relevant to nuclear reprocessing – by 2,2′:6′,2″-terpyridine (terpy)-type ligands, in synergistic combination with a liphophilic carboxylic acid coextractant, the PrIII/PhCO2-/NO3-/terpy reaction system h...

Investigation of the CuCl2/H2Memal/L (H2Memal=methylmalonic acid, L=1,10-phenanthroline or 2,2′-bipyridine) reaction system in MeOH and various molar ratios has lead to the isolation of two one-dimensional coordination polymers presenting the [Cu(L)(Memal)] repeating unit (1, L=1,10-phen; 2, L=2,2′-bpy). The Memal2− ligand adopts the bidentate [che...

The diferrous complex [Fe2(acpypentO)(NCO)3] (1),(acpypentO– = the anion of 1,5-bis[2-pyridyl(1-ethylimino)]pentane-3-ol) was studied by spectroscopic (dual-mode X-band EPR and 57Fe-Mössbauer) and magnetic (AC magnetic susceptibility) techniques. Complex 1 (A. K. Boudalis et al., Inorg. Chem.2004, 43, 1574) was previously shown to exhibit an intram...

A general method of increasing the ground-state total spin value of a polynuclear 3d-metal complex is illustrated through selected examples from cobalt(II) and nickel(II) cluster chemistry that involves the dianion of the gem-diol form of di-2-pyridyl ketone and carboxylate ions as organic ligands. The approach is based on the replacement of hydrox...