Molecular Sensors for Moisture Detection by Mössbauer Spectroscopy

A parameter of importance in various industrial and commercial applications is sensitivity to moisture. A new class of molecular sensors which enable the qualitative and quantitative determination of air moisture (high selectivity and sensitivity) by application of Mossbauer spectroscopy as the probe technique has been investigated. The electronic properties of the iron-containing sensor depend upon the presence of moisture which is taken up by it and this process is accompanied by a change in electronic spin ground state which can be detected by Mossbauer spectroscopy. The sensor is suitable for in-field and industrial application using the recently developed Mossbauer spectrometer MIMOS I…

Spin crossover in iron(II) tris(2-(2′-pyridyl)benzimidazole) complex monitored by variable temperature methods: synchrotron powder diffraction, DSC, IR spectra, Mössbauer spectra, and magnetic susceptibility

Abstract The thermal expansion of the spin crossover system [Fe(pybzim) 3 ](ClO 4 ) 2  · H 2 O (pybzim=2-(2 ′ -pyridyl)benzimidazole) has been determined from powder X-ray data between 50 and 250 K; the wavelength of the synchrotron source was 1.21888(1) A. The unit cell parameters of the triclinic crystal system were a =12.091 A, b =12.225 A, c =14.083 A, α =77.70°, β =80.35°, γ =74.35°, and V =1944.9 A 3 at 250 K. In addition to the linear thermal expansion of the unit cell volume, an extra expansion due to the low-spin (LS) to high-spin (HS) transition is observed. The V ( T ) function shows a sudden increase comparable with the step in the effective magnetic moment at the transition reg…

Hard-X-ray-induced excited-spin-state trapping.

Synthesis, crystal structure, EXAFS, and magnetic properties of catena [mu-tris(1,2-bis(tetrazol-1-yl)propane-N1,N1')iron(II)] bis(perchlorate). First crystal structure of an iron(II) spin-crossover chain compound.

[Fe(btzp)3](ClO4)2 (btzp = 1,2-bis(tetrazol-1-yl)propane) represents the first structurally characterized Fe(II) linear chain compound exhibiting thermal spin crossover. It shows a very gradual spin transition (T1/2 = 130 K) which has been followed by magnetic susceptibility measurements and 57Fe Mössbauer spectroscopy. The structure has been solved at 200 and 100 K by single-crystal X-ray analysis. It crystallizes in the trigonal space group P3c1 with Z = 2 Fe(II) units at both temperatures. The molecular structure consists of chains running along the c axis in which the Fe(II) ions are linked by three N4,N4' coordinating bis(tetrazole) ligands. The main difference between the two forms ap…

Strong Field Iron(II) Complex Converted by Light into a Long-Lived High-Spin State

Synthesis and immobilization of molecular switches onto titaniumdioxide nanowires

Abstract The precursor [Fe III (L)Cl (L =  N , N ′-bis(2′-hydroxy-3′-methyl-benzyliden)-1,7-diamino-4-azaheptane) is combined with [Mo(CN) 8 ] 4− yields a star shaped nona-nuclear cluster, [Mo IV {(CN)Fe III (L)} 8 ]Cl 4 . This Fe 8 Mo molecule is a high-spin system at room temperature. On cooling to 20 K some of the iron(III) centres in the molybdenum(IV)-star switch to the low-spin state as proven by Mossbauer spectroscopy. This molecule was deposited on TiO 2 nanowires by electrostatic interactions between the cluster cations and the surface functionalized titanium oxide nanowire. The synthesis and surface binding of the multistable molecular switch was demonstrated using IR and UV–Vis s…

Spin crossover in a tetranuclear Cr(III)-Fe(III)3 complex

A novel heteronuclear exchange-coupled complex [Cr I I I {(CN)Fe I I I -( 5 L)} 3 (CN) 3 ] containing a pentadentate blocking ligand 5 L was synthesized. The X-ray structure shows that a meridional isomer applies with inequivalent Fe I I I centers. The complex exhibits a thermally induced spin crossover along with the exchange coupling. Mossbauer spectra indicate a spin transition between S = ½ and S = 5/2 states although a considerable amount of Fe I I I centers stays high-spin at T = 6 K. The magnetization, the magnetic susceptibility, and the Mossbauer data were fitted in one run with a spin crossover model taking into account exchange interactions among all metal centers.

Unprecedented multistability in dodecanuclear complex compound observed by Mössbauer spectroscopy

Abstract The precursors [Fe(III)( 5X L)Cl] ( 5X LH 2  =  N , N ′-bis(1-hydroxy-2-benzyliden)-1,6-diamino-3-X-hexane, X = N,S) are high-spin ( S  = 5/2) complexes. This precursors are combined with the bridging unit [(NC) 5 Fe(II)-CN-Co(III)(CN) 5 ] 6− to yield star-shaped dodecanuclear clusters, [( 5X LFe(III)-NC) 5 Fe(II)-CN-Co(III)(CN-Fe(III) 5X L) 5 ]Cl 4 . The star-shaped compounds are high-spin systems at room temperature. On cooling to 20 K some of the iron(III) centers in the N-star switch to the low-spin state as proven by Mossbauer spectroscopy, i.e. multiple electronic transitions, while the S-star remains in the high-spin state.

Unprecedented multiple electronic spin transition in hepta- and nonanuclear complex compounds observed by Mössbauer spectroscopy

Abstract The precursor [Fe(III)(5L)Cl](5LH2 = N,N′-bis(1-hydroxy-2- benzyliden)-1,7-diamino-4-azaheptane) is a high-spin (S = 5/2) complex. This precursor combined with the bridging units [Fe(II)(CN)6]4−, [Co(III)(CN)6]3−, and [Mo(CN)8]4− yields starshaped hepta- and nonanuclear clusters, [Fe(II){(CN)Fe(III)(5L)}6]Cl2, [Co(III){(CN)Fe(III)(5L)}6]Cl3 and [Mo(IV){(CN)Fe(III)(5L)}8]Cl4. The starshaped compounds are high-spin systems at room temperature. On cooling to 20 K some of the iron(III) centers in the Co(III)- and Mo(IV)-star switch to the low-spin state as proven by Mossbauer spectroscopy, i.e., multiple electronic transitions, while the Fe(II)-star remains in the high-spin state.

Supramolecular Spintronic Devices: Spin Transitions and Magnetostructural Correlations in[Fe4IIL4]8+[2×2]-Grid-Type Complexes

The magnetism of a series of tetranuclear complexes of the [Fe4IIL4]8+ [2x2]-grid-type was investigated, revealing the occurrence of spin transition behavior within this class of compounds. The phenomenon depends directly on the nature of the substituent R(1) in the 2-position on the central pyrimidine group of the ligand L. All Fe(II) ions in compounds with R(1) substituents favoring strong ligand fields (R(1)=H; OH) remain completely in the diamagnetic low-spin state. Only complexes bearing R(1) substituents attenuating the ligand field by steric (and to a lesser extent electronic) effects (R(1)=Me; Ph) exhibit spin transition behavior triggered by temperature. In general, gradual and inc…

Molecular switching complexes with iron and tin as central atom

Abstract The precursor [Fe III (L)Cl] (LH 2  =  N , N ′-bis(2′-hydroxy-benzyliden)-1,6-diamino-3-N-hexane is a high-spin ( S  = 5/2) complex. This precursor is combined with the bridging units [Sn IV (X) 4 ] (X = CN − , NCS − ) to yield star-shaped pentanuclear clusters, [(LFe III –X) 4 Sn]Cl 4 . For X = CN − the 57 Fe-Mossbauer data show a multiple spin transition between iron(III) in the high-spin and low-spin state, while the 119m Sn-Mossbauer data indicate a valence tautomerism between Sn(IV) and Sn(II). Changing the bridging unit from X = CN − to X = NCS − turns the switchability off.

Stark-Feld-Eisen(II)-Komplex konvertiert durch Licht in einen langlebigen High-Spin-Zustand

Tuning the spin crossover above room temperature: iron(II) complexes of substituted and deprotonated 2,6-bis(benzimidazol-2-yl)pyridine

Abstract The complex [Fe(tzimpy)2](ClO4)2 · 2H2O (tzimpy = 2,4,6-tris-(benzimidazol-2-yl)pyridine) shows an abrupt spin crossover (S = 0–2 transition) above room temperature centered at Tc = 323 K with a hysteresis width of ΔT = 35 K. The neutral iron(II) complex with deprotonated bzimpy ligands (bzimpy = 2,6-bis(benzimidazol-2-yl)pyridine) exhibits a gradual spin transition on the first heating with Tc = 424 K. There are irreversible changes between T = 503 and 523 K: the liberation of the crystal water, the color change (blue–green) followed by a structure change. Next thermal cycles are reproducible though, heating/cooling paths are different from the first heating.

Pressure- and temperature-induced valence tautomeric interconversion in a o-dioxolene adduct of a cobalt-tetraazamacrocycle complex

An electronic switch at the molecular level has been realized by using a class of ionic compounds of the formula [Co(L)(diox)]Y (L = tetraazamacrocyclic ligand, Y = mononegative anion). Such compounds undergo temperature- and pressure-induced intramolecular one-electron transfer equilibria. The transition temperature of interconversion varies with the nature of the counterions Y (Y = PF6, BPh4, I). Surprisingly the effect of the anion on the transition temperature is not only governed by its volume but also by its coulombic interaction.

Mineralogy at Gusev Crater from the Mössbauer spectrometer on the Spirit Rover.

Mössbauer spectra measured on Mars by the Spirit rover during the primary mission are characterized by two ferrous iron doublets (olivine and probably pyroxene) and a ferric iron doublet (tentatively associated to nanophase ferric iron oxide). Two sextets resulting from nonstoichiometric magnetite are also present, except for a coating on the rock Mazatzal, where a hematite-like sextet is present. Greater proportions of ferric-bearing phases are associated with undisturbed soils and rock surfaces as compared to fresh rock surfaces exposed by grinding. The ubiquitous presence of olivine in soil suggests that physical rather than chemical weathering processes currently dominate at Gusev crat…

High-spin wheel of a heptanuclear mixed-valent Fe(II,III) complex.

Klimt artwork: red-pigment material investigation by backscattering Fe-57 Mössbauer spectroscopy, SEM and p-XRF

Material tests were performed on a rediscovered Klimt-artwork "Trompetender Putto". We performed studies on the red colored spots, mainly taken from non-restored parts. MIMOS II Fe-57 Mossbauer spectroscopy (novelty in art-pigment analysis) mainly reveals haematite and crystallized goethite in red colors. Electron microscopy can identify various layers of the original and overpainting of an artwork. The number of layers fluctuates between three and four chemically painted areas. The portable X-ray fluorescence analysis enables to reduce the pigment list to containing mercury (cinnabar), lead, zinc, iron and titanium. Infrared-light-irradiation visualizes the different age of the pigments.

A New Valence Tautomerism Example in an Electroactive Ferrocene Substituted Triphenylmethyl Radical

A new molecular system combining an open-shell organic radical that acts as an acceptor group, different from an o-quinone moiety, covalently linked to a ferrocene moiety, acting as the donor group, is shown to exhibit valence tautomerism.

Electronic Relaxation Phenomena Following 57Co(EC)57Fe Nuclear Decay in [MnII(terpy)2](ClO4)2·1/2H2O and in the Spin Crossover Complexes [CoII(terpy)2]X2·nH2O (X = Cl and ClO4):  A Mössbauer Emission Spectroscopic Study

The valence states of the nucleogenic 57Fe arising from the nuclear disintegration of radioactive 57Co by electron capture decay, 57Co(EC)57Fe, have been studied by Mossbauer emission spectroscopy (MES) in the 57Co-labeled systems:  [57Co/Co(terpy)2]Cl2·5H2O (1), [57Co/Co(terpy)2](ClO4)2·1/2H2O (2), and [57Co/Mn(terpy)2](ClO4)2· 1/2H2O (3) (terpy = 2,2‘:6‘,2‘ ‘-terpyridine). The compounds 1, 2, and 3 were labeled with ca. 1 mCi of 57Co and were used as the Mossbauer sources at variable temperatures between 300 K and ca. 4 K. [Fe(terpy)2]X2 is a diamagnetic low-spin (LS) complex, independent of the nature of the anion X, while [Co(terpy)2]X2 complexes show gradual spin transition as the temp…

Heptanuclear high-spin complex compounds based on S-donors

Abstract The precursors [Fe(III)( SY L)Cl] ( SY LH 2 ) =  N , N ′-bis(1-hydroxy-Y-2-benzyliden)-1,6-diamino-3-thiohexane, (Y = H, 3EtO, 5Me) are high-spin ( S  = 5/2) complexes. The precursors are combined with [Fe(II)(CN) 6 ] 4− and [Co(III)(CN) 6 ] 3− to yield star-shaped heptanuclear clusters, [Fe(II)(CN–Fe(III) SY L) 6 ]Cl 2 and [Co(III)(CN–Fe(III) SY L) 6 ]Cl 3 . The star-shaped compounds are high-spin (HS) systems at room temperature. On cooling to 20 K some of the iron(III) centers perform some HS–HS transition.

Anisotropic Effect after Stretching of the Spin-Crossover Compound [Fe(II)(2,6-bis-(benzimidazol-2′-yl)pyridine)2] (C1O4)2 in Polyvinylalcohol Polymer Matrix

Abstract [Fe(II)(2,6-bis-(benzimidazol-2′-yl)-pyridine)2](C1O4)2 diffused into a poly(vinyl)alcohol polymer matrix, exhibits an thermally induced spin-crossover. After stretching the matrix, the compound orients itself in the matrix. Polarised UV/VIS spectra measured parallel and perpendicular to the stretching direction allowed to calculate the distortion of the molecule in the matrix by means of semi-empirical PPP SCF-CI calculations.

Durch Temperatur, Druck oder Licht induzierter Spinübergang in einer supramolekularen Fe‐[2×2]‐Gitterverbindung

Effect of N-substitution in multinuclear complexes allows interplay between magnetic states and multistability investigated by Mössbauer spectroscopy

A series of pentadentate ligands N-X-5LH2 (X=H, Methyl, Benzyl)=N-X-saldptn (4-X-N,N′-bis(l-hydroxy-2-benzylidene)-1,7-diamino-4-azaheptane) has been prepared by a Schiff base condensation between 1,7-diamino-4-X-azaheptane and salicylaldehyde. Complexation with Fe(III) yields a series of high-spin (S=5/2) complexes of [FeIII(N-X-5L)Cl]. Such precursors were combined with [Mo(CN)8]4− and a series of blue nonanuclear cluster compounds [MoIV(CN)FeIII(N-X-5L)8]Cl4 resulted. Such star-shaped nonanuclear compounds are high-spin systems at room temperature. On cooling to 10K some of the iron(III) centers switched to the low-spin state as proven by Mossbauer spectra, i.e. multiple electronic trans…

Spin-Transition in [Fe(II)(2,6-Bis-(Benzimidazol-2′-yl)pyridine)2] (CIO4)2: Hysteresis Effect Dependent on the Matrix

Abstract Far-Infrared spectroscopical investigation of the spin-crossover in [Fe(II)(2,6-bis-(benzimidazol-2′-yl)-pyridine)2] (CIO4)2 exhibits a hysteresis in both CsI and polyethylene matrices within temperature cycles between 100K and 520K. The hysteresis broadening is dependent on the matrix and bigger in CsI. This can be explained due to polarity and hydrogen bonding. Two low spin vibrations, LS1 at 437 cm−1 and LS2 at 424cm−1, are observed. On heating from 100K to 520K: during LS1 decreases, the LS2 raises temporarily, until both LS1 and LS2 disappear; for the HS only one raising species was observed. This gives raise to assume two different sub-lattices.

Electronic Interactions in Ferrocene‐ and Ruthenocene‐Functionalized Tetraazamacrcocyclic Ligand Complexes of Fe II/III , Co II , Ni II , Cu II and Zn II

The syntheses of ferrocene- and ruthenocene-functionalized tetraazamacrocyclic ligands and their corresponding transition metal complexes are described. Reaction of N,N′-bis(2-aminoethyl)-1,3-propanediamine (2,3,2-tet) with 1,1′-diformylferrocene and 1,1′-diformylruthenocene produces the ligands fcmac and rcmac in 81−85% yield. Examination of their CuII, NiII, CoII, ZnII and FeII/III complexes by IR, UV/Vis, EPR and Mossbauer spectroscopy as well as by electrochemical studies suggests electronic communication between the two metal centers of each complex. The molecular structure of [CuII(fcmac)(FBF3)]BF4, determined by X-ray structure analysis, is reported and shows that the distance betwee…

LIESST Effect in Fe(II) 1,2,4-Triazole Chains

One-dimensional Fe(II) chains with 1,2,4-triazole as bridging ligands present the LIESST effect; i.e. their spin state switched from low-spin to high-spin after light irradiation at low temperature. This account summarizes the findings in this area of photomagnetism where 57Fe Mossbauer spectroscopy was used as a primary detection tool of the LIESST effect.

Synthesis, Structure, and Magnetic Properties of a Tris[3-(2-pyridyl)-1,2,4-triazole]iron(II) Spin-Crossover Complex

The synthesis and characterization of tris[3-(pyridin-2-yl)-1,2,4-triazole]iron(II) bis(tetrafluoroborate), obtained from the reaction of 3-(pyridin-2-yl)-1,2,4-triazole (Hpt) and hexaaquairon(II) tetrafluoroborate, [Fe(H2O)6](BF4)2, is described, together with its crystal structures at two temperatures. X-ray crystallographic parameters are as follows: [Fe(Hpt)3](BF4)2·nH2O (n ≈ 2) at 250 K: orthorhombic space group Pbam, a = 15.8068(18) A, b = 17.2800(14) A, c = 21.215(2) A, V = 5794.7(10) A3, and Z = 8. [Fe(Hpt)3](BF4)2·nH2O (n ≈ 2) at 95 K: orthorhombic space group Pbam, a = 15.7080(12) A, b = 17.1023(16) A, c = 21.006(2) A, V = 5643.1(9) A3, and Z = 8. The FeII ions are (at both temper…

Jarosite and hematite at Meridiani Planum from Opportunity's Mossbauer Spectrometer.

Mössbauer spectra measured by the Opportunity rover revealed four mineralogical components in Meridiani Planum at Eagle crater: jarosite- and hematite-rich outcrop, hematite-rich soil, olivine-bearing basaltic soil, and a pyroxene-bearing basaltic rock (Bounce rock). Spherules, interpreted to be concretions, are hematite-rich and dispersed throughout the outcrop. Hematitic soils both within and outside Eagle crater are dominated by spherules and their fragments. Olivine-bearing basaltic soil is present throughout the region. Bounce rock is probably an impact erratic. Because jarosite is a hydroxide sulfate mineral, its presence at Meridiani Planum is mineralogical evidence for aqueous proc…

ChemInform Abstract: Magnetic and Electronic Structure of the CMR Chalcospinel Fe0.5Cu0.5Cr2S4

Mössbauer mineralogy of rock, soil, and dust at Gusev crater, Mars: Spirit's journey through weakly altered olivine basalt on the plains and pervasively altered basalt in the Columbia Hills

The Moessbauer spectrometer on Spirit measured the oxidation state of Fe, identified Fe-bearing phases, and measured relative abundances of Fe among those phases for surface materials on the plains and in the Columbia Hills of Gusev crater. Eight Fe-bearing phases were identified: olivine, pyroxene, ilmenite, magnetite, nanophase ferric oxide (npOx), hematite, goethite, and a Fe(3+)-sulfate. Adirondack basaltic rocks on the plains are nearly unaltered (Fe(3+)/Fe(sub T) Px), and minor npOx and magnetite. Columbia Hills basaltic rocks are nearly unaltered (Peace and Backstay), moderately altered (WoolyPatch, Wishstone, and Keystone), and pervasively altered (e.g., Clovis, Uchben, Watchtower, …

Spin Crossover in a Supramolecular Fe4II [2×2] Grid Triggered by Temperature, Pressure, and Light

A multiplex electronic switch on the molecular level has been realized by using a tetranuclear FeII complex of the [2×2] grid type. The four metal ions can be switched stepwise between their high-spin and low-spin states by temperature, pressure, and light, thus representing a triple level, triple switch system as illustrated in the picture.

Spin crossover in mononuclear and binuclear iron(III) complexes with pentadentate Schiff-base ligands

Abstract A series of mononuclear hexacoordinate iron(III) complexes, [Fe( 5 L )(py)]BPh 4 , and binuclear hexacoordinate iron(III) complexes, [( 5 L )Fe(μ 2 -bpy)Fe( 5 L )](BPh 4 ) 2 , has been prepared and their magnetic properties were investigated; the pentadentate ligands were derivatives of 5 L =saldptn=N,N′-bis(2-hydroxybenzyliden)-1,7-diamino-4-azaheptane. Temperature variation of the effective magnetic moment for them shows that a spin transition from the low-spin to the high-spin state occurs. The magnetic data were fitted to an Ising-like model appropriate for the mono- and binuclear systems.

Iron(III) Complexes on a Dendrimeric Basis and Various Amine Core Investigated by Mössbauer Spectroscopy

Dendrimers of various generations were synthesized by the divergent method. Starting from various amine cores (G0a, G0b, G0c) the generations were built by reaction of the amine with acrylnitrile followed by hydrogenation with DIBAL-H. Treatment with salicylaldehyde creates a fivefold coordination sphere for iron in the molecular periphery. The resulting multinuclear coordination compounds are investigated by Mossbauer spectroscopy.

Spin transition in heptanuclear star-shaped iron(III)–antimony(V) NCS- and CN-bridged compounds

Abstract The precursor [FeIII(L)Cl] (LH2 = N,N′-bis(2′-hydroxy-benzyliden)-1,6-diamino-3-azahexane) has been prepared and Mossbauer spectroscopy assigned a high-spin (S = 5/2) state at room temperature. The precursor is combined with the bridging units [SbV(X)6]− (X = CN−, NCS−) to yield star-shaped heptanuclear clusters [(LFeIII–X)6SbV]Cl5. The star-shaped compounds are in general high-spin systems at room temperature. On cooling to 20 K some of the iron(III) centers switch to the low-spin state as indicated by Mossbauer spectroscopy, i.e. multiple electronic transitions. While the cyano-bridged complex performs a multiple spin transition the thiocyanate-compound shows no significant popul…

The Nonanuclear [Mo(IV) {(CN)Fe(III)(3-ethoxy-saldptn)}8]Cl4 Complex Compound Exhibits Multiple Spin Transitions Observed by Mössbauer Spectroscopy

The pentadentate ligand 3-EO-5LH2 = 3-ethoxy-saldptn = N,N′-bis(3-ethoxy-1-hydroxy-2-benzyliden)-1,7-diamino-4-azaheptane has been prepared by a Schiff base condensation between 1,7-diamino-4-azaheptane and the corresponding 3-ethoxy-salicyaldehyde. 3-EO-5LH2 is a sterical extention to 5LH2. Its complexation with Fe(III) gave the high-spin (S = 5/2) complex of [Fe(III)(3-EO-5L)Cl]. This precursor was combined with [Mo(CN)8]4− and a blue nonanuclear cluster [Mo(IV){(CN)Fe(III)(3-EO-5L)}8]Cl4 resulted. This starshaped nonanuclear compound is a high-spin system at room temperature. On cooling to 10 K some of the eight iron(III) centers switched to the low-spin state as proven by Mossbauer spec…

Mössbauer Spectroscopic Study and Magnetic Investigation of Iron(III) Complexes on a DendrimericBasis

The functionalization of the molecular surface of various dendrimer generations with a phosphorous core and external amine groups is obtained by converting those amine groups into the corresponding imines of salicylaldehyde creating multiple coordination sites for the iron atoms. Treatment with iron(III) chloride yields multinuclear iron(III) complexes on a dendrimeric basis.The obtained multinuclear molecular systems exhibit extremely high total spin values. The influence of the generation growth on this type of coordination compounds is investigated by Mossbauer spectroscopy and SQUID magnetometry.

Induktion langlebiger angeregter Spinzustände durch harte Röntgenstrahlung

Mössbauer mineralogy of rock, soil, and dust at Meridiani Planum, Mars: Opportunity's journey across sulfate-rich outcrop, basaltic sand and dust, and hematite lag deposits

Additonal co-authors: P Gutlich, E Kankeleit, T McCoy, DW Mittlefehldt, F Renz, ME Schmidt, B Zubkov, SW Squyres, RE Arvidson

Structure of the copper (II) perchlorate complex with Schiff base ligand containing pyridine N-oxide fragments and propylene bridges: Solvatochromic effect

Abstract The copper (II) perchlorate complexes with Schiff base ligands were investigated by X-ray single crystal analysis, electron spectroscopy, infrared and electron paramagnetic spectroscopy. The Schiff bases were obtained as condensation products of 2-pyridinecarboxaldehyde N-oxide with dipropylenetriamine (L1) and triethylenetetramine (L3), respectively. The structure of the complex [CuL2](ClO4)2 was solved. In the structure, the ligand exists in the form of aliphatic polyamine containing two Schiff bases in contrary to the free form of this ligand with one pyrimidine ring and one Schiff base. Electronic spectra of the copper (II) perchlorate complexes of both ligands in different sol…

A heptanuclear Fe(II)–Fe(III)6 system with twelve unpaired electrons

Abstract The pentadentate ligand 5 LH2 = saldptn = N,N′-bis(1-hydroxy-2-benzyliden)-1,7-diamino-4-azaheptane has been prepared by a Schiff base condensation between 1,7-diamino-4-azaheptane and the corresponding salicyaldehyde. Its complexation with Fe(III) gave the high-spin (S=5/2) complex of [Fe III ( 5 L)Cl]. This precursor was combined with [Fe(CN)6]4− and a blue heptanuclear complex [FeII{(CN)Fe III ( 5 L)}6]Cl2 resulted. This system belongs to the class of high-spin molecules possessing twelve unpaired electrons (S=6) as proven by the magnetic susceptibility measurements and Mossbauer spectra.