Macrocycle-Based Spin-Crossover Materials

International audience; New iron(II) complexes of formula [Fe(L1)](BF(4))(2) (1) and [Fe(L2)](BF(4))(2) x H(2)O (2) (L1 = 1,7-bis(2'-pyridylmethyl)-1,4,7,10-tetraazacyclododecane; L2 = 1,8-bis(2'-pyridylmethyl)-1,4,8,11-tetraazacyclotetradecane) have been synthesized and characterized by infrared spectroscopy, variable-temperature single-crystal X-ray diffraction, and variable-temperature magnetic susceptibility measurements. The crystal structure determinations of 1 and 2 reveal in both cases discrete iron(II) monomeric structures in which the two functionalized tetraazamacrocycles (L1 and L2) act as hexadentate ligands; the iron(II) ions are coordinated with six nitrogen atoms: four from …

Spin crossover properties of the [Fe(PM-BiA)2(NCS)2] complex - phases I and II

International audience; In the present review, we reexamine the photomagnetic properties of the [Fe(PM-BiA)2(NCS)2], cis-bis(thiocyanato)-bis[(N-2'-pyridylmethylene)-4-(aminobiphenyl)]iron(II), compound which exhibits, depending on the synthetic method, an exceptionally abrupt spin transition (phase I) with a very narrow hysteresis (T1/2O = 168 K and T1/2N = 173 K) or a gradual spin conversion (phase II) occurring at 190 K. In both cases, light irradiation in the tail of the 1MLCT-LS absorption band, at 830 nm, results in the population of the high-spin state according to the light-induced excited spin-state trapping (LIESST) effect. The capacity of a compound to retain the light-induced HS…

New planar polynitrile dianion and its first coordination polymer with unexpected short M⋯M contacts (tcno2−=[(NC)2CC(O)C(CN)2]2−)

International audience; A new planar polynitrile dianion ([tcno]2− = [(NC)2CC(O)C(CN)2]2−) has been synthesized as its potassium salt, K2[tcno] (1). The crystallization of 1 by the slow evaporation of an aqueous solution at room temperature gave two types of colourless crystals having two different shapes [1-A: fine plates and 1-B: needles] for which the crystal structure determinations showed similar geometries for the polynitrile anion in both the structures. The combination of this novel dianion with Cu(II) led to the coordination complex [Cu(tcno)2(H2O)2] (2), which constitutes the first coordination complex of this dianion. The structure of 2 can be described as a coordination polymer …

Hepta- and tetra-nuclear copper(II) clusters self-assembled by cyano- and azacyano-carbanions

International audience; Two polynuclear copper(II) complexes with hydroxido-bridging ligands and polycyanide units, [Cu{Cu(tn)}6(μ2-OH)2(μ3-OH)4Cl2](tcm)4Cl2·2H2O (1) and [{Cu(bpy)}4(OH)4(dca)2](dca)2·bpy·2H2O (2) (tn = NH2(CH2)3NH2; tcm− = [C(CN)3]−, bpy = 2,2′-bipyridyl, dca− = [N(CN)2]−) have been prepared by one-pot reactions. The structure of 1 consists of a centrosymmetric heptanuclear ion [Cu{Cu(tn)}6(μ2-OH)2(μ3-OH)4Cl2]6+. The tcm− and the halide anions which appear as counter-ions in the formula unit, play an important role in the stabilization of the complex since the hydrogen bonding between nitrogen atoms of the tcm− anion and halide anions, and hydrogen atoms of the terminal wa…

Polynitrile anions as ligands: From magnetic polymeric architectures to spin crossover materials

International audience; The use of polynitrile anions as ligands (L) either alone or in combination with neutral co-ligands (L′) is a very promising and appealing strategy to get molecular architectures with different topologies and dimensionalities thanks to their ability to coordinate and bridge metal ions in many different ways. The presence of several potentially coordinating nitrile groups (or even other donor groups as –OH, –SH or –NH2), their rigidity and their electronic delocalization allow the synthesis of original magnetic high dimensional coordination polymers with transition metals ions. Furthermore, these ligands have shown coordinating and bridging capabilities in novel discr…

Photoinduced HS state in the first spin-crossover chain containing a cyanocarbanion as bridging ligand

A new polymeric approach, based on cyanocarbanion ligands, for the design of spin crossover (SCO) compounds led us to the compound [Fe(abpt)2(tcpd)] (1) (tcpd^2 = (C[C(CN)2|3)^2 , abpt = 4-amino-3,5-bis(pyridin-2-yl)-1,2,4-triazole) which has been characterised as the first SCO molecular chain involving a cyanocarbanion as bridging ligand. Gomez Garcia, Carlos Jose, Carlos.Gomez@uv.es

Syntheses, structural characterisation and magnetic properties of Fe(ii) and Mn(ii) compounds with the pentacyanopropenido ligand; structural characterisation of a substituted pyrazolo[1,5-a]pyrimidine

International audience; Reactions between the metal(II) salts [M(CH3CN)n](BF4)2 (M = Fe, n = 6; M = Mn, n = 4) and some organic anionic polynitriles were studied. With the pentacyanopropenide anion pcp− [pcp− = (NC)2CC(CN)C(CN)2−], were obtained, according to the experimental conditions, the new complexes [M(pcp)2(H2O)4] (1, M = Fe; 2, M = Mn) and [M(pcp)2] (3, M = Fe; 4 = Mn). Use of the hexacyano-3,4-diazahexadienediide anion [(NC)2CC(CN)NNC(CN)C(CN)22−] instead of pcp− did not afford polynitrile metal complexes but led to a new organic derivative 5, of formula C10N8H2. Crystallographic studies indicated that the isostructural compounds 1 and 2 involve discrete monomeric units with pcp li…

Cyanocarbanion-based spin-crossover materials: photocrystallographic and photomagnetic studies of a new iron(II) neutral chain

International audience; A new iron(II) chain of formula [Fe(abpt)(2)(tcpd)] [1; (tcpd)(2-) = [C(10)N(6)](2-) = (C[C(CN)(2)](3))(2-) = 2-dicyanomethylene-1,1,3,3-tetracyanopropanediide anion, abpt = 4-amino-3,5-bis(pyridin-2-yl)-1,2,4-triazole] has been synthesized and characterized by IR spectroscopy, detailed variable-temperature single-crystal X-ray diffraction, magnetic and photomagnetic measurements. The crystal structure determination of 1 reveals a one-dimensional structural architecture in which the (tcpd)(2-) cyanocarbanion acts as a μ(2)-bridging ligand and the two abpt molecules act as chelating ligands. Detailed X-ray diffraction studies as a function of the temperature (293-10 K…

New coordination polymer based on a triply bridged dicarboxylate ligand: Synthesis, structure, and magnetic properties of the adipato complex [Cu4(bpy)4(adip)3](tcnoet)2·2H2O {bpy=C10H8N2; adip2−=[O2C(CH2)4CO2]2−; tcnoet−=[(NC)2CC(OEt)C(CN)2]−}

International audience; One-pot reaction of copper(II) chloride dihydrate CuCl2 · 2H2O with 2,2′-bipyridyl (bpy = C10H8N2) in the presence of sodium adipate Na2adip (adip2− = [O2C(CH2)4CO2]2−) and potassium 1,1,3,3-tetracyano-2-ethoxypropenide (tcnoet− = [(NC)2CC(OEt)C(CN)2]−) gives the new compound [Cu4(bpy)4(adip)3](tcnoet)2 · 2H2O (1), which was characterized by single crystal X-ray diffraction analysis. The Cu(II) metal ion presents an elongated square pyramidal CuN2O3 environment, with an oxygen atom in apical position and a base plane involving almost equivalent bond lengths. The structure can be described as a pseudo dinuclear species in which two Cu(bpy) units are triply bridged by …

Guidelines to design new spin crossover materials

International audience; This review focuses on new families of spin crossover (SCO) complexes based on polynitrile anions as new anionic ligands or on polyazamacrocycles as neutral macrocyclic ligands. We have shown that the structural and electronic characteristics (original coordination modes and high electronic delocalization) of the polynitrile anions can be tuned by slight chemical modifications such as substitution of functional groups or variation of the negative charge to design new discrete or polymeric SCO systems.In our ongoing work on the design of new molecular systems based on new ligands that can be fine-tuned via chemical modifications, another promising way which has been r…

Front Cover: Magnetic Bistability in Macrocycle‐Based Fe II Spin‐Crossover Complexes: Counter Ion and Solvent Effects (Eur. J. Inorg. Chem. 34/2016)

Polymorphism and Metallic Behavior in BEDT-TTF Radical Salts with Polycyano Anions

Up to five different crystalline radical salts have been prepared with the organic donor BEDT-TTF and three different polynitrile anions. With the polynitrile dianion tcpd2− (=C[C(CN)2]32−), two closely related radical salts: α'-(ET)4tcpd·THF (1) (THF = tetrahydrofurane) and α'-(ET)4tcpd·H2O (2) have been prepared, depending on the solvent used in the synthesis. With the mono-anion tcnoetOH− (=[(NC)2CC(OCH2CH2OH)C(CN)2]−) two polymorphs with similar physical properties but different crystal packings have been synthesized: θ-(ET)2(tcnoetOH) (3) and β''-(ET)2(tcnoetOH) (4). Finally, with the mono-anion tcnoprOH− (=[(NC)2CC(OCH2CH2CH2OH)C(CN)2]−) we have prepared a metallic…

CCDC 1060081: Experimental Crystal Structure Determination

Related Article: Smail Triki, Eric Milin, Carlos J. Gómez-García, Samia Benmansour, Mathieu Marchivie|2015|Polyhedron|98|18|doi:10.1016/j.poly.2015.05.037