Synthesis and Physical Properties of K4[Fe(C5O5)2(H2O)2](HC5O5)2·4H2O (C5O52– = Croconate): A Rare Example of Ferromagnetic Coupling via H-bonds
The reaction of the croconate dianion (C(5)O(5))(2-) with a Fe(III) salt has led, unexpectedly, to the formation of the first example of a discrete Fe(II)-croconate complex without additional coligands, K(4)[Fe(C(5)O(5))(2)(H(2)O)(2)](HC(5)O(5))(2)·4H(2)O (1). 1 crystallizes in the monoclinic P2(1)/c space group and presents discrete octahedral Fe(II) complexes coordinated by two chelating C(5)O(5)(2-) anions in the equatorial plane and two trans axial water molecules. The structure can be viewed as formed by alternating layers of trans-diaquabis(croconato)ferrate(II) complexes and layers containing the monoprotonated croconate anions, HC(5)O(5)(-), and noncoordinated water molecules. Both …
Synthesis, crystal structures and magnetic properties of mononuclear tris(croconate)ferrate(III) complexes
Abstract A straightforward synthetic method to prepare mononuclear croconato-containing iron (III) complexes, (A)3[Fe(C5O5)3] [A = tetrabutylammonium = n-Bu4N+ (1) and tetraphenylphosphonium = PPh 4 + ( 2 ) ; C 5 O 5 2 - = croconate = dianion of 4 , 5 - dihydroxycyclopent - 4 - ene - 1 , 2 , 3 - trione ] along with their crystal structures and magnetic properties, are reported. The Fe(III) atom adopts a pseudo-octahedral geometry while magnetic susceptibility measurements, in the 2–300 K temperature range, show the occurrence of a high spin state (S = 5/2) in both complexes.
New BEDT-TTF/[Fe(C5O5)3]3- Hybrid System: Synthesis, Crystal Structure, and Physical Properties of a Chirality-Induced α Phase and a Novel Magnetic Molecular Metal
The paramagnetic and chiral anion [Fe(C5O5)3]3- (C5O52-=croconate) has been combined with the organic donor BEDT-TTF (=ET=bis(ethylenedithio)tetrathiafulvalene) to synthesize a novel paramagnetic semiconductor with the first chirality-induced alpha phase, alpha-(BEDT-TTF)5[Fe(C5O5)3].5H2O (1), and one of the few known paramagnetic molecular metals, beta-(BEDT-TTF)5[Fe(C5O5)3].C6H5CN (2). Both compounds present layers of BEDT-TTF molecules, with the alpha or beta packing modes, alternating with layers containing the high-spin S=5/2 Fe(III) anions and solvent molecules. In the alpha phase, the alternation of the chiral [Fe(C5O5)3]3- anions along the direction perpendicular to the BEDT-TTF cha…
Molecular materials with conducting and magnetic properties based on ET and [ M(tdas)2]x-dithiolenes
Two hybrid molecular materials showing a combination of magnetic and conducting properties, the charge-transfer (ET) 2 [Fe(tdas) 2 ] (1) and (ET)Ni(tdas) 2 (2), (ET=bis(ethylenedithio) tetrathiafulvalene; M=Fe, Ni; tdas=l,2,5-thiadiazole-3,4-dithiolate) salts, are characterized by vibrational (IR and Raman) and UV-VIS-NIR spectroscopies. These studies have proved to be effective and diagnostic tools in identifying the oxidation state (partial or integer) and the packing pattern (dimers or segregated stacks) of the ET donor only, since no v(C=C) group vibration sensitive to the charge of M(tdas) 2 complexes has been observed. This is ascribed to the extensive electron-delocalization inside t…
A chirality-induced alpha phase and a novel molecular magnetic metal in the BEDT-TTF/tris(croconate)ferrate(iii) hybrid molecular system
The novel paramagnetic and chiral anion [Fe(C5O5)3]32 has been combined with the organic donor BEDT-TTF (= ET = bis(ethylenedithio)tetrathiafulvalene) to yield the first chirality- induced α phase and a paramagnetic metal. Gomez Garcia, Carlos, Carlos.Gomez@uv.es ; Coronado Miralles, Eugenio, Eugenio.Coronado@uv.es ; Gimenez Saiz, Carlos, Carlos.Gimenez@uv.es
Synthesis, Structure, Spectroscopic Studies and Magnetic Properties of the Tetrakis(5,7‐dichloro‐8‐quinolinolato)gadolinium(III) Complex
The synthesis and structural characterization of the neutral gadolinium tetrakis-type complex with 5,7-dichloro-8-quinolinolato (H5,7ClQ) ligands, [Gd(5,7ClQ)2(H5,7ClQ)2Cl], is reported. The GdIII ion is epta coordinated to one chloride ion and to four ligands: two N,O-chelated monoanions and two as zwitterionic (+NH and O–) monodentate oxygen donors. Electronic and vibrational spectra provide suitable markers to distinguish the presence of deprotonated and protonated ligands. The magnetic behaviour of this compound was investigated and explained by taking into account that π–π stacking interactions between the (H5,7ClQ) ligands give rise to a ferromagnetic interaction between the gadoliniu…
New BDH-TTP/[MIII(C5O5)3]3– (M = Fe, Ga) Isostructural Molecular Metals
Two new isostructural molecular metals-(BDH-TTP)(6)[M(III)(C(5)O(5))(3)]·CH(2)Cl(2) (BDH-TTP = 2,5-bis(1,3-dithiolan-2-ylidene)-1,3,4,6-tetrathiapentalene, where M = Fe (1) and Ga (2))-have been prepared and fully characterized. Compound 1 is a molecular conductor showing paramagnetic behavior, which is due to the presence of isolated [Fe(C(5)O(5))(3)](3-) complexes with high-spin S = (5)/(2) Fe(III) metal ions. The conductivity originates from the BDH-TTP organic donors arranged in a κ-type molecular packing. At 4 kbar, compound 1 behaves as a metal down to ∼100 K, showing high conductivity (∼10 S cm(-1)) at room temperature. When applying a pressure higher than 7 kbar, the metal-insulator…
A New Conducting Molecular Solid Based on the Magnetic [Ni(dmf)6]2+ Cation and on [Ni(dsit)2]22− (dsit=1,3-dithiole-2-thione-4,5-diselenolate) Showing an Unprecedented Anion Packing
The synthesis, X-ray structure, magnetic and transport properties of the compound Ni(dmf) 6 [Ni(dsit) 2 ] 2 (dmf=dimethylformamide, dsit = 1,3-dithiole-2-thione-4,5-diselenolate) are described. This compound crystallizes in the monoclinic space group P2 1 /c, with a = 18.709(6), b = 22.975(5), c = 20.418(5) A, β = 99.31(2)° and Z = 6; its structure consists of [Ni(dsit) 2 ] 2- 2 dimers and isolated [Ni(dmf) 6 ] 2+ cations both centrosymmetric and non-centrosymmetric. The dimers are packed forming chains along the [101] direction with short Se...Se interdimer contacts. Additional interchains S...S contacts render this structure a three-dimensional character, never observed so far in other [N…