Jean-Pascal Sutter

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• PhD
• Research Director at French National Centre for Scientific Research

A cyano-bridged Fe(II)−Cr(III) single-chain magnet designed to ensure a parallel orientation of the axial anisotropy of the building units is reported. This ferromagnetic chain compound consists of a pentagonal bipyramid Fe(II) complex with Ising-type anisotropy and a dicyanide Cr(III) complex interlinked through their apical positions. It is chara...

A procedure that enabled rational access to the first example of hybrid material made of NPs grown within a H‐bonded framework is reported. To avoid competitive reactions with the framework units, the metal precursor was chemically trapped in the porous structure and subsequently photo‐reduced to afford the hybrid material Ag@SPA‐2, which consists...

A Ni(II) complex harnessed in a pentagonal bipyramidal environment by a rigid N5-macrocyclic ligand (i.e. 1,3,10,12-tetramethyl-1,2,11,12-tetraaza[3](2,6)-pyridino[3](2,9)-1,10-phenanthrolinophane-2,10-diene) is shown to exhibit axial anisotropy with a ZFS D parameter in the order of −10 to −15 cm⁻¹, and this anisotropy is not significantly changed...

The magnetic anisotropy associated with a pentagonal bipyramidal (PBP) coordination sphere is examined on the basis of experimental and theoretical investigations. The origin and the characteristics of this anisotropy are discussed in relation to the electronic configuration of the metal ions. The effects of crystal field, structural distortion, a...

Five isostructural microporous supramolecular architectures prepared by H‐bonded assembly between the hexa‐anionic complex [Zr2(Ox)7]⁶⁻ (Ox=oxalate, (C2O4)²⁻) and tripodal cations (H3‐TripCH2‐R)³⁺ with R=H, CH3, OH and OBn (Bn=CH2Ph) are reported. The possibility to obtain the same structure using a mixture of tripodal cations with different R grou...

Solvothermal conditions enable the formation of polynuclear Co(II) compounds with 4′‐[p‐(Imidazol‐1‐yl)phenyl]‐2,2′:6′,2′′‐terpyridine (L) acting as a bridging ligand. 1D coordination polymer [Co2(L)2(Cl)4].5H2O, 1, and discrete [Co2(L)(Cl)4(DMF)]2, 2, can be selectively obtained by tuning the CoCl2/L ratio involved in the reaction. A peculiar feat...

Pentagonal bipyramidal complexes with a first-order spin–orbit coupling contribution can be readily obtained by chemical design optimization.

Chiral 1D coordination compounds formed by association of either of the enantiomers of [ML(MeOH)Cl]Cl (with M=MnII or FeII; L stands for either R or S enantiomer of a pentadentate macrocycle) and NBu4[FeIII(bpb)(CN)2], namely: 1D‐[{FeIII(bpb)(CN)2}{MII(LR)}](PF6) and 1D‐[{FeIII(bpb)(CN)2}{MII(LS)}](PF6) with M=Mn (2R, 2S) and Fe (3R, 3S). The bis(t...

Two new 2p–3d complexes, (Et3NH)[ML(hfac)2], have been obtained using the nitronyl-nitroxide radical (HL) derived from 2-hydroxy-3-methoxy-5-nitrobenzaldehyde (M = Mn 1; Co 2). The two compounds are isomorphous and their structures consist of anionic mononuclear species, [M(hfac)2L]⁻, M = Mn 1; Co 2, and triethylammonium cations, Et3NH⁺. The metal...

With the aim of tuning the magnetic anisotropy, a series of Co(ii) complexes with the general formula of complex cations [Co(L)X]⁺, where X = Br⁻ (1); I⁻ (2); NCO⁻ (3); NCS⁻ (4a); N3⁻ (5), and [Co(L)(NCS)2] (4b), (L = a 17-membered pyridine-based N3O2-macrocyclic ligand containing two pyridin-2-ylmethyl pendant arms) were prepared and thoroughly ch...

A novel series of one-dimensional coordination polymers (CPs) is achieved via a facile one-pot synthetic strategy employing the nitrate salts of trivalent lanthanides, a pentadentate chelating ligand, and triphenylphosphine oxide...

Lanthanide metal organic framework compounds, [Ln(BPTA)1.5(Bpy)]·H2O; Ln = Y, Eu, Gd, Tb, Dy (1a-5a) and [Ln(BPTA)1.5(Phen)]·H2O; Ln = Y, Eu, Gd, Tb, Dy (1b-5b) were prepared employing 2,5-bis(prop-2-yn-1-yloxy)terephthalic acid (2,...

Large uniaxial magnetic anisotropy, expressed by a negative value of the axial zero-field splitting parameter D, has been achieved in a series of trigonal prismatic Co(II) complexes with general formula [Co(L)X]Y, where L = 1,5,13,17,22-pentaazatricyclo[15.2.2.17,11]docosa-7,9,11(22)-triene, X = Cl–(1a,b), Br–(2), N3–(3), NCO–(4), NCS–(5), NCSe–(6)...

Employing the new nitronyl nitroxide biradical ligand biNIT-3Py-5-Ph (2-(5-phenyl-3-pyridyl)-bis(4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide)), a 16-spin Cu-radical complex, [Cu8(biNIT-3Py-5-Ph)4(hfac)16] 1, and three 2p-3d-4f chain complexes, {[Ln(hfac)3][Cu(hfac)2]2(biNIT-3Py-5-Ph)2}n (LnⅢ= Gd 2, Tb 3, Dy 4; hfac = hexafluoroacetylacetonate), h...

The reaction of nitronyl nitroxide biradical NITPhMeImbis [5‐(2‐methylimidazole)‐1,3‐bis(1‐oxyl‐3’‐oxido‐4’,4’,5’,5’‐tetramethyl‐4,5‐hydro‐1H‐imidazol‐2‐yl)‐benzene] with Ln(hfac)3 ⋅ 2H2O and Cu(hfac)2 (hfac=hexafluoroacetylacetonate), led to two series of 2p–3d‐4f complexes, namely, nona‐spin clusters, [Ln2Cu3(hfac)12(NITPhMeImbis)2] (Ln=Gd 1, Dy...

A chiral 3D coordination compound, [Gd2(L)2(ox)2(H2O)2], arranged around a dinuclear Gd unit has been characterized by X-ray photoemission and X-ray absorption measurements in the context of density functional theory studies. Core level photoemission of the Gd 5p multiplet splittings indicates that spin orbit coupling dominates over j-J coupling ev...

We report the synthesis of [(L)DyIII(Cy3PO)2]·[BPh4] (1-Dy) (where H2L = 2,6-diacetylpyridine bis-benzoylhydrazone and Cy = cyclohexyl) which crystallized in the triclinic, P1̄ space group. The local geometry around Dy(III) in 1-Dy was found to be pentagonal bipyramidal (pseudo-D5h). The AC magnetic susceptibility measurements performed on 1-Dy and...

A pentadentate‐[N3O2] ligand, H2LNMe2, formed by condensation of diacetyl pyridine and dimethylcarbamoyl hydrazide (i. e. Me2NCONHNH2), is reported to yield mononuclear pentagonal bipyramidal (PBP) metal complexes with CrIII, MnII, FeII, CoII, and NiII, that exhibit good solubility in a wide range of solvents as compared to the classically used H2L...

Each enantiomer of a chiral pentagonal bipyramidal (PBP) Fe(II) complex ([Fe(LN5R,R)Cl(MeOH)]Cl.H2O, 1R, or [Fe(LN5S,S)Cl(MeOH)]Cl.H2O, 1S.) have been obtained using either the R or the S stereoisomer of the macrocyclic pentadentate ligand formed in a template-condensation reaction of the tetraamine N,N′-Bis-{(1R,2R)-[2-(amino)]cyclohexyl}-1,2-diam...

New lanthanide carboxylate compounds with two- (2D) and three-dimensional (3D) structures have been prepared by employing 2,5-bis(prop-2-yn-1-yloxy)terephthalic acid (2,5-BPTA) as an organic linker. The compounds, [Ln(C14H8O6)(C7O3H4)·2H2O]·4(H2O), Ln = Y, Pr, Nd, Sm, Eu, Gd, Tb, Dy and [Ln(C7O3H4)3·(C3H7ON)·(H2O)]·2(H2O)(C3H7NO), Ln = La, Ce, Pr,...

Applications of quantum information science (QIS) generally rely on the generation and manipulation of qubits. Still, there are ways to envision a device with a continuous readout, but without the entangled states. This concise perspective includes a discussion on an alternative to the qubit, namely the solid-state version of the Mach-Zehnder inter...

A series of air-stable mononuclear octacoordinate Ln(III) complexes, [(L)Ln(TPPO)3]OTf (Ln = Y (1·Y); Gd (1·Gd); Tb (1·Tb); Dy (1·Dy); Ho (1·Ho); and Er (1·Er)) and [(L)Ln(TPPO)(NO3)] (Ln = Y (2·Y) and Dy (2·Dy)), are synthesized employing a rigid N3O2-pentadentate chelating ligand as the basis ligand and meridional ancillary ligands (where H2L = 2...

A new nitronyl‐nitroxide ligand (H2L) featuring alcoholic and phenolic groups has been synthesised starting from 2‐hydroxy‐3‐(hydroxymethyl)‐5‐methylbenzaldehyde (A). Using this ligand, three 2p–4 f binuclear complexes have been obtained and crystallographically characterized: [Ln2(HL)2(hfac)4], (Ln=Gd 1, Tb 2, Dy 3). Apart from the desired compoun...

Four novel heptanuclear Ln-Cu complexes with the formula [Ln2Cu(hfac)8(NITPhTzbis)2][LnCu(hfac)5(NITPhTzbis)]2 (LnCu = YCu 1, TbCu 2, DyCu 3 and HoCu 4; hfac = hexafluoroacetylacetonate) were successfully constructed by employing the triazole functionalized nitronyl nitroxide biradical ligand NITPh-Tzbis (NITPh-Tzbis = 5-(1,2,4-triazolyl)-1,3-bis(1...

Serendipitous self-assembly is a potential approach in achieving structurally versatile and unexpected solids with chosen metal-ligand combinations. Cyclen (1,4,7,10-tetraazacyclododecane) is an interesting flexible molecule, well explored for biological and material...

A series of heterometallic compounds based on the association of trans‐dicyanido Cr(III) complex [Cr(L)(CN)2]K ⋅ 2H2O and several divalent [MnII(H2Lⁿ)Cl2] heptacoordinated complexes, where Lⁿ stands for pentadentate ligands featuring a planar N3O2 coordination pocket and various substituents (NH2, cyclohexyl, S,S‐mandelic), is described. A dinuclea...

Trinuclear systems of formula [{Cr(LN3O2Ph)(CN)2}2M(H2LN3O2R)] (M=MnII and FeII, LN3O2R stands for pentadentate ligands) were prepared in order to assess the influence of the bending of the apical M−N≡C linkages on the magnetic anisotropy of the FeII derivatives and in turn on their Single‐Molecule Magnet (SMM) behaviors. The cyanido‐bridged [Cr2M]...

The preparation, crystal structures, and magnetic properties of a family of hetero-tri-spin 1-D coordination polymers with the formula [Ln(hfac)3Cu(hfac)2(4-NIT-MePyz)2] (Ln = Gd, 1, Tb, 2, Dy, 3; hfac = hexafluoroacetylacetonate; 4-NIT-MePyz = 2-{4-(1-methyl)-pyrazolyl}-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) are reported. In these complexe...

New members of stuffed tridymite structure, Ba(Zn/Co)1‐xSi1‐xM2xO4 (M = Al3+ and Fe3+) were shown to exhibit multiferroic behavior. The compounds were SHG active, exhibit ferroelectric as well as ferromagnetic behavior. Read more in the Full Paper by S. Natarajan et al. on page 1995.

Two mononuclear complexes [(Et3NH)[M(hfac)2L] (M = Ni, 1; Zn, 2) have been synthesized using a nitronyl-nitroxide radical substituted nitrophenol, that is 2-(2-hydroxy-3-methoxy-5-nitrophenyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-3-oxide-1-oxyl, HL, as a proligand. The crystal structures of 1 and 2 have been solved and indicate an octahedral...

The stuffed tridymite structure Ba(Zn/Co)1−xSi1−xM2xO4 (M=Al³⁺ and Fe³⁺) is explored for the possible multiferroic behavior and to develop new inorganic colored materials. The compounds were synthesized by employing conventional solid‐state chemistry methods in the temperature range 1100–1175 °C for 24 h. The powder X‐ray diffraction (PXRD) and Rie...

A simple approach to impart water processability in cyanido bridged extended structures are described. A chiral cyanido bridged Co( ii )–Fe( iii ) extended structure is assembled and its water processability is demonstrated.

Circularly polarized luminescence (CPL) was evidenced for the first time in single crystals of a chiral-at-metal Dy(III) single-molecule magnet. This CPL is opposite for the enantiomers and was found to appear and become stronger at lower temperatures when the relaxation of the magnetization for the Dy centers is slower. The luminescence dissymmetr...

We report Peacock–Weakley complexes, Na9[Ln(W5O18)2]∙35H2O, formed with Tm(III), 1, and Yb(III), 2. Their syntheses, physico-chemical characterizations, crystal structures, and magnetic properties are described. Ab initio calculations are also reported. These polyoxometalate (POM) complexes were obtained using original synthetic conditions where ac...

One-dimensional coordination polymers constructed with the 4d metallo-ligand [Mo(NCS)6]3- associated with NiII and CoII complexes are reported. The first series consists of anionic NCS-bridged [Mo-MII]- coordination polymers associated with a discrete paramagnetic complex or a diamagnetic CoIII complex acting as cations. The latter takes advantage...

A series of neutral homologous complexes [(L)Ln(Cy3PO)Cl] {where Ln = Gd (1), Tb (2), Dy (3), and Er (5)} and [(L)Dy(Ph3PO)Cl] (4) [H2L = 2,6-diacetylpyridine bis-benzoylhydrazone] were isolated. In these complexes, the central lanthanide ion possesses a pentagonal bipyramidal geometry with an overall pseudo D5h symmetry. The coordination environme...

Three biradical-bridged heterometallic chains, [LnCu2(hfac)7(bisNITPhPy)]n (LnIII = Gd, 1; Tb, 2; Ho, 3), were synthesized by means of nitronyl nitroxide biradical bisNITPhPy ([5-(4-pyridyl)-1,3-bis(1'-oxyl-3'-oxide-4',4',5',5'-tetramethyl-4,5-hydro -1H-imidazol-2-yl)]benzene; hfac = hexafluoroacetylacetonate). In these structures, the bisNITPhPy b...

The ability of a sulfonyl amidophosphate (SAPh) compounds having the structural fragment RSO2NHP(O)R to act as a β‐diketone homologue for the complexation of Ln(III) ions has been explored. We report the synthesis and magnetic properties of five mononuclear complexes of formula LnL3Phen (L stands for deprotonated bis(methyl(phenyl)amino)phosphoryl)...

By the proper choice of the substituents on the aldehyde and amine groups, the nature of the Schiff base formed (fully condensed or half condensed) can be tuned by the templating effect of the metal ion. The condensation of 5-chlorosalicylaldehyde with ethylene diamine in the presence of Co(II) or Cu(II) cations and azido anions has afforded two ne...

A biradical with ferromagnetic intramolecular interaction was found to improve the SCM behavior of a nitronyl nitroxide-Cu-Dy chain, resulting in an energy barrier for magnetization reversal of 40 K.

Spins in molecular magnets can experience both anisotropic exchange interactions and on-site magnetic anisotropy. In this paper, we study the effect of exchange anisotropy on the molecular magnetic anisotropy both with and without on-site anisotropy. When both the anisotropies are small, we find that the axial anisotropy parameter DM in the effecti...

Multi-dentate nitronyl nitroxide radical Nit-Ph-3,5-bIm (Nit-Ph-3,5-bIm=2-[3,5-bis(1-imidazole)-phenyl]-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) reacted with Co(hfac)2·2H2O or Cu(hfac)2 to yield two novel 3d-radical complexes {[Co(hfac)2]2(Nit-Ph-3,5-bIm)}n1 and {[Cu(hfac)2]7(Nit-Ph-3,5-bIm)3}n2 (hfac- = hexafluoroacetylacetonate). In both co...

Spins in molecular magnets can experience both anisotropic exchange interactions and on-site magnetic anisotropy. In this paper we study the effect of exchange anisotropy on the molecular magnetic anisotropy both with and without on-site anisotropy. When both the anisotropies are small, we find that the axial anisotropy parameter $D_M$ in the effec...

Three unprecedented lanthanide (Ln)-radical loop chains have been obtained by employing multidentate pyridyl- or triazole-substituted nitronyl nitroxide ligands. Two dysprosium complexes exhibit distinct slow relaxation of magnetization due to the subtle change of the local ligand field of the Dy ion.

Two-dimensional hetero-tri-spin 2p-3d−4f coordination polymers involving Co(II) and Ln(III) ions assembled by a polydentate paramagnetic nitronyl nitroxyde ligand are reported. [Ln(hfac)3{Co(hfac)2}2(NITPhPyrim)2] (LnIII = Gd 1, Tb 2; hfac = hexafluoroacetylacetonate, NITPhPyrim = 2-[4-(5-pyrimidyl)phenyl]-4,4,5,5- tetramethylimidazoline-1-oxyl-3-o...

Air-stable pentagonal-bipyramid Ln(III) complexes with a rigid equatorial plane is synthesized rationally by employing a pentadentate chelating ligand. The Dy(III) analogue exhibits single-ion-magnet behavior with Ueff = 70 K under Hdc = 500 Oe.

A series of heptacoordinated CrIII complexes with either cyano or thiocyanato ligands in the apical positions are described and their ability to act as metallo-ligands is illustrated. These compounds contain a pentadentate ligand, H2LN3O2R [H2LN3O2R = 2,6-diacetylpyridinebis(benzoylhydrazone) for R = Ph, 2,6-diacetylpyridinebis(4-biphenylylcarbonyl...

Ester-functionalized bi-compartmental Schiff-base ligand and their 3d-Ln complexes with 3d = Ni(II), Cu(II) or Zn(II) and Ln = Gd(III), Tb(III) or Dy(III) are reported. The modularity of the Schiff-base structure (i.e. symmetric vs dissymmetric, ester-group) is illustrated to highlight the possibility offered by the ester for facile functionalizati...

Copper and nickel azide compounds with one- and two-dimensional structures were synthesized and characterized. Magnetic studies indicate antiferromagnetic behaviour. The figure highlights the two different role of the azide as the bridging ligand, observed in the structures. Details are discussed in the article by Subhradeep Mistry et al on page 17...

Four new copper complexes viz., [{Cu(2-aminopyridine)(N3)2(H2O)}2]n (1), [Cu3(3-aminopyridine)2(N3)6]n (2) [{Cu(3-aminopyridine)(N3)2}2]n (3), and [Cu(4-aminopyridine)2(N3)2]n (4), have been synthesized with isomeric aminopyridines viz., 2-aminopyridine (2-ap), 3-aminopyridine (3-ap), and 4- aminopyridine (4-ap), to probe the role of ligand and rea...

Ladder-type and chain 2p-3d-4f complexes based on a bridging nitronyl nitroxide radical, namely, [LnCu(hfac)5(NIT-Ph-p-OCH2trz)]·0.5C6H14 [Ln = Y (1a), Dy (1b)] and [LnCu(hfac)5(NIT-Ph-p-OCH2trz)] [Ln = Y (2a), Dy (2b); NIT-Ph-p-OCH2trz = 2-[4-[(1H-1,2,4-triazol-1-yl)methoxy]phenyl]-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide; hfac = hexafluoroac...

Three new azide based compounds have been synthesized employing aliphatic amines as site blocking agents: [Ni(N3)(C6H16N2)2]ClO4 (I) [C6H16N2 = N,N′-diethylethylenediamine (DEDA)], [Cu8(N3)18(C6H18N4)2] (II) [C6H18N4 = Tris(2-aminoethyl) amine(TREN)] and [Cu7(N3)14(C7H19N3)2].2H2O (III) [C7H19N3 = 3,3′-Diamino-N-methyldipropylamine (DMDA)]. The com...

Off-charge-stoichiometry assemblage of ionic H-bond donors and acceptors was found to be a straightforward approach to a hydrogen-bonded open framework with pores decorated by basic sites. The supramolecular architecture exhibits 1-nm-wide channels functionalized by pyridyl groups and high accessible voids (53 %).Remarkable affinity was achieved fo...

An hydrogen-bonded open framework with pores decorated by pyridyl groups has been constructed following an off-charge-stoichiometry assemblage of protonated tetrakis(4-pyridyl-oxymethyl)methane and [Al(oxalate)3]3-, respectively the H-bond donor and acceptor of the ionic H-bond interactions. This supramolecular porous architecture (SPA-2) possesses...

Single molecule magnets (SMMs) with single-ion anisotropies $\mathbf d$, comparable to exchange interactions J, between spins have recently been synthesized. In this paper, we provide theoretical insights into the magnetism of such systems. We study spin chains with site spins, s=1, 3/2 and 2 and on-site anisotropy $\mathbf d$ comparable to the exc...

Single molecule magnets (SMMs) with single-ion anisotropies $\mathbf d$, comparable to exchange interactions J, between spins have recently been synthesized. In this paper, we provide theoretical insights into the magnetism of such systems. We study spin chains with site spins, s=1, 3/2 and 2 and on-site anisotropy $\mathbf d$ comparable to the exc...

Pentagonal bipyramid Fe(II) complexes have been investigated in order to evaluate their potential as Ising-spin building units for the preparation of hetero-polynuclear complexes that are likely to behave as SMMs. The considered monometallic complexes result from association of a divalent metal ion with pentadentate ligands having 2,6-diacetylpyrid...

A series of protonated polyamine derivatives have been considered as H-bond donor units for the construction of extended networks by assemblage with the anionic metal-oxalate complex [Z(C2O4)4]4− by means of charge-assisted H-bonds. In order to evaluate the parameters that favor the formation of 3D open-framework architectures, linear, flexible and...

A copper(II) complex with ethylene diamine and azide, viz., [Cu2(en)2(N3)4]n has been isolated under self-assembling conditions and characterized both structurally and magnetically in order to probe the role of reactant molar ratios in generating supramolecular assemblies with strong magnetic interactions towards achieving molecule-based magnets as...

Syntheses and magnetic behavior of bis(trimethylsilyl)amido tricyclopentylphosphane complexes [M{N(SiMe3)2}2(PCyp3)] of manganese(II), iron(II), and cobalt(II) are described. Crystal structures for this series of rare phosphane adducts of homoleptic bis(trimethylsilyl)amide complexes have been solved. The Fe and Co derivatives have been found to po...

A new synthetic procedure was developed to obtain a novel mononuclear chiral square-pyramidal (acetato)bis(aminoalkoxido)MnIII complex from a heterometallic ZnII/MnII system with a crucial role for O2 in the process. The resulting compound was characterized spectroscopically and crystallographically, and its magnetic properties were determined. The...

The polynuclear compounds containing anisotropic metal ions often exhibit efficient barriers for blocking of magnetization at fairly arbitrary geometries. However, at variance with mononuclear complexes, which usually become single-molecule magnets (SMM) under the sole requirement of a highly axial crystal field at the metal ion, the factors influe...

A family of four-coordinate Fe(II) complexes formed with N,N'-chelating amido-pyridine ligands was synthesized, and their magnetic properties were investigated. These distorted tetrahedral complexes exhibit significant magnetic anisotropy with zero-field splitting parameter D ranging between -17 and -12 cm(-1). Ab initio calculations enabled identi...

Utilizing a new ferrocene-based compartmental ligand, H4L (1), a series of novel heterometallic complexes [{LZn(μ-OAc)Dy}4(μ4-H2O)] (2), [{LZn(μ-OAc)Tb}4(μ4-H2O)] (3), [{LZn(μ-OAc)Ho}4(μ4-H2O)] (4), [L = Fe[(C5H4){-C(Me)[double bond, length as m-dash]N-N[double bond, length as m-dash]C6H3-(o-O)(m-O)}]2] were synthesized and characterized. 2 and 3 c...

A novel ester-functionalized bi-compartmental Schiff-base ligand and its dinuclear Zn-Ln complexes [Ln = Dy (1), Tb (2), Gd (3)] are reported herein. Athough electron-withdrawing substituents at the para position of the phenol moieties do not change the coordination environment of the Ln centers in comparison with the nonfunctionalized ligand, they...

The reactions of Ln(NO3)3·5H2O (Ln = Dy3+, Tb3+, Ho3+, Er3+) and a multidentate flexible ligand, (E)-N′-[2-hydroxy-3-(hydroxymethyl)-5-methylbenzylidene]-6-(hydroxymethyl)picolinohydrazide (LH4), in the presence of Et3N in a 1:1:3 molar ratio afforded a series of complexes [Ln4(LH2)4(µ2-OH)4]·xCH3OH·yH2O (Dy3+, x = 2, y = 2; Tb3+, x = 4, y = 5; Ho3...

The promising magnetic behaviors of heterospin systems have spurred on the research of 2p-3d-4f hetero-tri-spin compounds. Such magnetic system has crucial advantages: the strongest possible magnetic interactions resulting from the direct binding of the radicals to the metal ions, access to strong magnetic anisotropies arising from 4f ions, and nov...

Magnetic bistability spanning over a temperature domain of 40 K can result from a small structural deformation of the gadolinium aminoxyl coordination. This is illustrated for a nitronyl nitroxide 3d-4f chain, [Ln(hfac)3Cu(hfac)2(NIT-Pyrim)2] (Ln(III) = Gd, Dy), which is the first example of a bistable lanthanide-based complex.

Two new azide bridged copper (II) coordination polymer compounds, [Cu7(N3)14(C3H10N2)(C4H13N3)]n (I) and [Cu7(N3)14(C3H10N2)(C5H15N3)2]n (II) [where C3H10N2 = 1,2-diaminopropane (1,2-DAP); C4H13N3 = diethylenetriamine (DETA); C5H15N3 = N-2-aminoethyl-1,3-propanediamine (AEDAP)] were prepared employing a room temperature diffusion technique involvin...

Preparation, crystal structures and magnetic properties of a series of four binuclear Cu–Ln complexes are reported (Ln = GdIII, TbIII, and DyIII). These are based on a bicompartmental Schiff-base ligand formed by condensation of 1,3-diaminopropan-2-ol with ortho-vanillin. This Schiff-base is known to usually involve its deprotonated alcohol group i...

Novel hetero-tri-spin coordination polymers formed of ring-shaped Cu-nitronyl nitroxide spin clusters and Ln(III) linkers are reported. These mixed 2p-3d-4f compounds of formula {[Ln(hfac)3][Cu(hfac)2(NIT-3Py)]2·C6H14}n [Ln(III) = Y (1), Gd (2), Tb (3), and Dy (4); NIT-3Py = 2-(3-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide; hfac = hexa-f...

Supramolecular assemblages based on anionic H-acceptors and cationic H-donors have been envisioned to elaborate open frameworks maintained by ionic H-bonds. Combinations of di-anionic chloranilate (CA2−), oxalate (Ox2−), or terephthalate (BDC2−) and trisimidazolium or tetrapyridinium derivatives (three and four N–H+ donors, respectively) yielded fi...

Efficient preparation of composite materials consisting of ZIF-8 nanocrystals embedded inside the channels of macroporous anodic aluminum oxide membranes is reported. 1-D self-supported ZIF-8 superstructures are recovered through matrix dissolution. (Figure Presented).

Three families of heterotrimetallic chains (Type 1 - Type 3), with different topologies, have been obtained by reacting the 3d-4f complexes, [{Cu(L1)}xLn(NO3)3] with x = 1 or 2, formed in situ by reaction of Schiff-base bi-compartmental [CuII(L1)] complexes and lanthanide(III) salts, with (NHBu3)3[M(CN)8] (M = MoV, WV). For type 1 series of compoun...

Rare case of genuine (i.e. field-free) SMM has been found for mixed 3d-4f-5d ring-shaped compounds with Tb(III) (Ueff/kB = 23.0 K) or Dy(III) (Ueff/kB = 26.4 K). The ferromagnetic interactions between the transition metals are shown to play an essential role in this feature

The reaction of a new compartmental ligand, H3L [H3L = N′-(2-hydroxy-3-methoxybenzylidene)-2-(-2-hydroxy-3-methoxybenzylideneamino)benzohydrazide], with lanthanide salts followed by reaction of MnII salts in presence of triethylamine along with pivalic acid afforded heterometallic hexanuclear complexes, [{LMn(Cl)(μ3-OH)Gd2(μ3-OH)(μ-Piv)2}2·3MeCN·7M...

Supramolecular organization of a metal complex may significantly contribute to the magnetization dynamics of mononuclear SMMs. This is illustrated for a heptacoordinated Fe(ii) complex with rather moderate Ising-type anisotropy for which a slow magnetization relaxation with significant energy barrier was reached when this complex was properly organ...

Hydrogen-bond assembly of tripod-like organic cations [H3-MeTrip]3+ (1,2,3-tri(4′-pyridinium-oxyl)-2-methylpropane) and the hexa-anionic complex [Zr2(oxalate)7]6− leads to a structurally, thermally, and chemically robust porous 3D supramolecular framework showing channels of 1 nm in width. Permanent porosity has been ascertained by analyzing the ma...

Employing nitronyl nitroxide lanthanide(III) complexes as metallo-ligands allowed the efficient and highly selective preparation of three series of unprecedented hetero-tri-spin (CuLn-radical) one-dimensional compounds. These 2p-3d-4f spin systems, namely [Ln3 Cu(hfac)11 (NitPhOAll)4 ] (Ln(III) =Gd 1Gd , Tb 1Tb , Dy 1Dy ; NitPhOAll=2-(4'-allyloxyp...

Bimetallic Schiff-base Al(3+) complexes bearing ester functions at the periphery of the ligands are shown to be efficient fluorescent chemosensors for picric acid detection. The prominent role of an association between the chemosensor and the picric acid in the detection process is demonstrated. The detection of picric acid in water is achieved wit...

Five new complexes, viz., [Ni(2-aminomethylpyridine)2(N3)2] (1), [Cu(2-aminomethylpyridine)(N3)2]n (2), [Cu(2-aminomethylpyridine)2(N3)2] (3), [Cu3(3-aminomethylpyridine)2(N3)6]n (4) and [Zn(2-aminomethylpyridine)2(N3)2] (5), were synthesized and structurally characterized to probe the role of temperature as well as ligand geometry in the formation...

The reaction of lanthanide(III) chloride salts (Gd(III), Dy(III), Tb(III), and Ho(III)) with the hetero donor chelating ligand N'-(2-hydroxy-3-methoxybenzylidene)-6-(hydroxymethyl)picolinohydrazide (LH3) in the presence of triethylamine afforded the hexanuclear Ln(III) complexes [{Ln6(L)2(LH)2}(μ3-OH)4][MeOH]p[H2O]q[Cl]4·xH2O·yCH3OH (1, Ln = Gd(III...

A novel approach for the preparation of hetero-tri-spin magnetic compounds is described. It consists in using preformed metal-nitronyl nitroxide complexes as metallo-ligands in an assembling process involving an additional metal centre. This is illustrated by two unprecedented radical-Cu-Ln chain compounds (Ln = Gd(3+), Tb(3+)).

Two heteronuclear NCS-bridged compounds, namely [(Cu(3,3,3-tet)(CH3CN))(2){Mo(NCS)(6))}][Mo(NCS)(6)] [PPh4](2)center dot 6CH(3)CN (1) and [{Cu(3,3,3-tet)(CH3CN)}(4)(Mo(NCS)(6)}][Mo(NCS)(6))(3)[Cu(3,3,3-tet)(CH3CN)](2) (2) (with 3,3,3-tet = N,N-bis(3-aminopropyl)-1,3-propanediamine) have been synthesized and their crystal structures were characteriz...

A homometallic Zr(IV)-oxalate three-dimensional (3-D) coordination polymer of formula [Zr(OH)2(C2O4)·0.5H2O] is reported. This compound was found to be a microporous solid with reversible sorption abilities. Upon guest release and sorption, the crystalline material undergoes single crystal to single crystal transitions. The crystal structures for t...

Supramolecular assemblages between three different [Zr(A)4]4− metallotectons (A stands for oxalate, Ox2−; dihydrobenzoquinonate, DBQ2−; or chloranilate CA2−) and three different guanidinium cation analogues (guanidinium, H-Guan+; 2-amino-imidazolium, H-AIm+; and N,N-dimethylguanidinium, H-DmG+) have been envisioned to investigate how the anionic an...

The reaction of the lanthanide(III) salts [Dy(III), Tb(III), and Gd (III)] with a hetero donor chelating ligand N'-(2-hydroxy-3-methoxybenzylidene)-6-(hydroxymethyl) picolinohydrazide (LH3) and pivalic acid (PivH) in the presence of tetra-n-butylammonium hydroxide (TBAH) afforded the tetranuclear Ln(III) coordination compounds, [Ln4(LH)2(LH2)2(μ2-η...