RESUMEN

The chiral TTF-based donor molecule bis(2'-hydroxylpropylthio)(ethylenedithio)tetrathiafulvalene (BHPT-EDT-TTF) has produced enantiopure R,R and S,S radical-cation salts with polyiodide anions I3- and I82-. Enantiomorphic 6 : 6 donor : I3 phases grown from either the R,R or S,S donor are semiconducting with similar activation energies of 0.24-0.30 eV and 0.22-0.23 eV, respectively, and contain three unique face-to-face donor pairs whose relative orientation is determined by side chain conformations and hydrogen bonding. Racemic material under the same conditions gave an insulating centrosymmetric phase with R,R and S,S donor cations in a face-to-face pair partnered with an octaiodide dianion, and with a ca. 3 : 1 disorder between the enantiomers. Enantiopure BHPT-EDT-TTF yielded two further insulating crystalline phases of composition 2 : 2 with triiodide and 2 : 1 with octaiodide.

RESUMEN

The first radical-cation salts in the extensive family (BEDT-TTF)x[(A)M(C2O4)3]·Guest containing lithium as the counter cation have been synthesized and characterised.

RESUMEN

The structure and properties of a new semiconducting BEDT-TTF-based charge-transfer salt containing the ferrocenesulfonate (Fc-SO3(-)) anion, α-(BEDT-TTF)2Fc-SO3·2.5H2O, are described. The structure and magnetic properties of a zwitterion of ferrocenesulfonate, Fc(+)-SO3(-), are also reported.

RESUMEN

While an addition product was formed by the reaction of AZADO (2-azaadamantane N-oxyl) with TCNQF4 (2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane), the reaction of AZADO with thiourea provided an inclusion compound, in which AZADO molecules are incorporated in cylindrical channels formed by thiourea molecules.

RESUMEN

Several 1,4-benzoquinone derivatives carrying oxy-TEMPO radical(s) at the 2-position or 2,5-positions were found to give black crystals by recrystallization from pale yellow solutions and it was revealed from their crystal structures that unusual single-component CT complexes were formed, in which a nitroxide moiety plays the roll of a donor part and a 1,4-benzoquinone group of the same molecule works as an acceptor part, respectively. On the contrary, no CT formation was found for the derivatives carrying oxy-TEMPO radicals at 2,6-positions and one of the TEMPO groups contributes to a CT formation in a 1,4-benzoquinone derivative carrying amino-TEMPO radicals at 2,5-positions derived from fluoranil, while the other one has a close oxygen-to-oxygen contact with another neighboring molecule to give a very large exchange coupling of J/k(B) = -154 K.

RESUMEN

Three kinds of molecular complexes based on tetrathiafulvalene (TTF) and dialkylviologens were prepared and their crystal structures elucidated. While TTF-dimethylviologen complex forms a mixed stack arrangement of donors and acceptors in its crystal structure, TTF donors aggregate with long alkyl groups by CH/pi and/or van der Waals interactions in a couple of TTF-heptylviologen complexes.

Asunto(s)

RESUMEN

A new bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF)-based salt with a ferrocenyl moiety, alpha' ''-(BEDT-TTF)(4)(Fe(C(5)H(4)SO(3))(2)).6H(2)O, has been prepared. The ferrocenyl part of this salt is neutral and diamagnetic, but the magnetic susceptibility is well modeled by a Curie-Weiss law with C = 0.142 emu.K.mol(-1) (approximately 1/3 of s = 1/2 spin). The spin is likely to be localized on the donor layer because of its unique charge disproportionation.

RESUMEN

Over the last decades scientists have faced growing requirements in novel methods of fast and sensitive analysis of antioxidant status of biological systems, spin redox probing and spin trapping, investigation of molecular dynamics, and of convenient models for studies of photophysical and photochemical processes. In approaching this problem, methods based upon the use of dual chromophore-nitroxide (CN) compounds have been suggested and developed. A CN consists of two molecular sub-functionality (a chromophore and a stable nitroxide radical) tethered together by spacers. In the dual compound the nitroxide is a strong intramolecular quencher of the fluorescence from the chromophore fragment. Reduction to hydroxylamine, oxidation of the nitroxide fragment or addition of an active radical yield the fluorescence increase and the parallel decay of the fragment electron spin resonance (ESR) signal. At certain conditions the dual molecules undergo photomagnetic switching and form excited state multi-spin systems. These unique properties of CN were intensively exploited as the basis for several methodologies, which include molecular probing, modeling intramolecular photochemical and photophysical processes, and construction of new magnetic materials.

RESUMEN

Several trans-azobenzene derivatives carrying a nitroxide (aminoxyl) radical (2a, 6a-12a) were prepared, and their photoisomerization reactions to the corresponding cis-isomers were investigated. Although no fruitful results could be obtained for the photoisomerizations of the derivatives with para-subsituents (9a-12a), the unsubstututed derivatives at the para-position (2a, 6a, 7a, 8a) were found to show photoisomerizations by irradiation to give the corresponding cis-isomers (2b, 6b, 7b, 8b), being isolated as relatively stable solid materials, and the change of the intermolecular magnetic interactions was apparently observed by the structural change for each photochromic couple.

RESUMEN

The pressure-induced electrical conductivity properties of beta-(BDA-TTP)2I3 have been investigated; the salt exhibits a dramatic change in the conductivity behaviour above ca. 10 kbar and undergoes a superconducting transition with an onset near 10 K.

RESUMEN

A trans-azobenzene derivative with a long alkyl chain and a TEMPO radical showed photo-induced isomerization to become the corresponding cis-isomer with a significant change of its intermolecular magnetic interaction from a weak ferromagnetic one based on the CW model to a relatively strong antiferromagnetic one based on the ST model with the J-value of 36.7 K.

RESUMEN

Recent studies on the exploitation of novel organic radical compounds that exhibit photo-responsive properties by illumination are described in this tutorial review. Those so far reported consist of a variety of photo-responsive pi-electron moieties such as azobenzene, diarylethene, biindenylidene, terphenoquinone, anthracene, naphthopyran, arylimine, or hexaarylbiimidazoles, bearing stable organic radicals or generating organic radicals as spin centres for magnetic properties. The switching behaviours of their magnetic properties evoked by the stimuli of irradiation are discussed by taking the associated structural changes into consideration.

Asunto(s)

RESUMEN

Three conducting BEDT-TTF charge-transfer salts with tris(oxalato)metallate anions have unit cells containing both[small alpha] and [small beta][double prime] donor packing motifs.

RESUMEN

Three N-salicylideneamine derivatives bearing TEMPO (2,2,6,6-tetra- methyl-1-piperidinyloxy) substituents were prepared in order to study their structure and property relationships and to investigate the possibilities of the existence of heat and/or light responsive magnetic properties. Curie-Weiss behavior with weak ferromagnetic intermolecular spin-spin interactions was observed in one of the radicals, while antiferromagnetic interactions were predominant for the other radicals and the structure-property relationships were investigated for the radical compounds from their crystal structures obtained by X-ray analyses. Preliminary results of the examination of their responses towards light and heat are also described.

Asunto(s)

RESUMEN

The preparation, crystal structure and physical properties of beta-(BDA-TTP)2GaCl4 has been investigated; the salt exhibits superconductivity at 3.1 K (onset) under a hydrostatic pressure of 7.6 kbar.

RESUMEN

The title compound, C(24)H(20)P(+).C(9)H(17)NO(5)S(-), consists of an organic monovalent cation and an organic monovalent anion, the latter being derived from the TEMPO radical (TEMPO is 2,2,6,6-tetramethylpiperidin-1-oxyl). Two inversion-related anions interact via two -O-H.O-S- hydrogen bonds, forming a dimer in which there are no short contacts between the spin centres (-N-O) of the TEMPO(OH)SO(3)(-) anions. Furthermore, no significant magnetic interaction is observed between the dimers because the dimer is surrounded by cations. These results are consistent with the paramagnetic behaviour of the title salt.

RESUMEN

[reaction: see text] Naphthopyran derivatives with aminoxyl substituents (4a,b) gave the corresponding open-formed isomers (5a,b) by irradiation, which could be changed back to the starting closed-formed naphthopyrans by the treatment with SiO(2) as a catalyst. The tuning of intermolecular magnetic interactions between the isomer couples was found to be possible in these reversible systems.

RESUMEN

Series of aminoxyl radicals (TEMPO or nitronyl nitroxide radicals) bearing phenyl benzoate, troponoid, or biphenylcarbonitrile as mesogenic cores with long alkyl substituents were prepared. Although most aminoxyl radicals showed only weak antiferromagnetic interactions due probably to the remote spin centers as clarified by the X-ray analysis of 4a and no appreciable mesogenic phase was observed in each compound, an unusual magnetic transition from an original Curie-Weiss phase to another magnetic phase well-expressed by a singlet-triplet (ST) model was disclosed through the thermal transition in the 4'-undecyloxy-4-biphenylcarbonitrile derivative with oxocarbonyl-TEMPO 12b.

RESUMEN

The synthesis and electrochemical properties of the DHDA-TTP donor, a hybrid of 2,5-bis(1,3-dithiolan-2-ylidene)-1,3,4,6-tetrathiapentalene (BDH-TTP) and 2,5-bis(1,3-dithian-2-ylidene)-1,3,4,6-tetrathiapentalene (BDA-TTP), has been investigated, and its ability to form metallic cation-radical salts is elucidated.