The 1-D polymeric structure of the [Fe(NH2trz)3](NO3)2·nH2O (with n = 2) spin crossover compound proven by single crystal investigations.

The first single crystal-based description of a spin transition compound from the patented [Fe(Rtrz)(3)]X(2)·nH(2)O family is reported, properly the compound with Rtrz = 4-amino-1,2,4-triazole, X = NO(3) and n = 2. This study definitively proves the 1-D polymeric nature of the crystal structure and allows a description of the [Fe(Rtrz)(3)] chains, as well as of the anions and water implementation within the crystal lattice opening the possibility of subsequent investigations of the structure-property correlation within this peculiar family of spin transition compounds.

Modulation of the luminescence quantum efficiency for blue luminophor {Al(salophen)}(+) by ester-substituents.

A series of Al(III) complexes of a salophen (N,N'-bis(salicylidene)-o-phenylenediamine) derivative with an ester substituent at the C5 position of the salicylidene rings have been prepared and their luminescence properties investigated. All exhibit a bright blue emission (lambda(em) = 478 nm) that is observed neither for other metal ions nor with the non-functionalized ligand. Moreover, the ester-R group (Me, (t)Bu, Ph) was found to significantly affect the quantum yields (varphi = 12 to 20%) of the luminophor. DFT calculations have been undertaken to reveal the influence of the ester and its R-group on the frontier molecular orbitals. Preparation and photoluminescence properties in solution and solid state are reported. The crystal structure of a pyridine oxide adduct [L(tBu)Al(PyO)(2)].NO(3), where L(tBu) stands for the tButyl-ester functionalized Schiff base, has been solved.

Nanoparticles of [Fe(NH2-trz)3]Br2.3H2O (NH2-trz=2-amino-1,2,4-triazole) prepared by the reverse micelle technique: influence of particle and coherent domain sizes on spin-crossover properties.

This paper describes the synthesis of iron(II) spin-crossover nanoparticles prepared by the reverse micelle technique by using the non-ionic surfactant Lauropal (Ifralan D0205) from the polyoxyethylenic family. By changing the surfactant/water ratio, the size of the particles of [Fe(NH2-trz)3]Br2.3H2O (with NH2trz=4-amino-1,2,4-triazole) can be controlled. On the macroscopic scale this complex exhibits cooperative thermal spin crossovers at 305 and 320 K. We find that when the size is reduced down to 50 nm, the spin transition becomes gradual and no hysteresis can be detected. For our data it seems that the critical size, for which the existence of a thermal hysteresis can be detected, is around 50 nm. Interestingly, the change of the particle size induces almost no change in the temperature of the thermal spin transition. A systematic determination of coherent domain size carried out on the nanoparticles by powder X-ray diffraction indicates that at approximately 30 nm individual particles consist of one coherent domain.

Nanoporous magnets of chiral and racemic [{Mn(HL)}2Mn{Mo(CN)7}2] with switchable ordering temperatures (TC = 85 K <--> 106 K) driven by H2O sorption (L = N,N-dimethylalaninol).

Molecule-based solids represent a rare opportunity to combine, adjust, and interrelate structural and physical functionalities to develop multifunctional materials. Here we report on a series of porous supramolecular magnets whose magnetic properties are related to their sorption state. A family of magnets of the formula [{Mn(HL)(H2O)}2Mn{Mo(CN)7}2].2H2O have been obtained by assembling the heptacyano-metalate building unit {Mo(CN)7}4- with Mn(II) in the presence of protonated N,N-dimethylalaninol (L) as ligand, the latter being either as a racemic mixture or as a chiral R- or S-enantiomer. The resulting magnets possess an open framework structure and exhibit a TC with a switching behavior (TC = 85 K <--> 106 K) as a function of the hydration state. Moreover, chiral magnets are formed with the optically active ligands. The H2O and gas (N2, CO2, CO) sorption features, the magnetic behavior of both the hydrated and dehydrated magnets, and the crystal structures of the hydrated chiral (S) and racemic magnets are described.

A reversible metal-ligand bond break associated to a spin-crossover.

The [Fe(II)L(CN)(2)].H(2)O complex, dicyano[2,13-dimethyl-6,9-dioxa-3,12,18-triazabicyclo[12.3.1]octadeca-1(18),2,12,14,16-pentaene]iron(II) monohydrate, exhibits a thermal induced metal-ligand bond break reversible in the solid state and associated to a spin crossover that corresponds to an unprecedented structurally characterized modification of the coordination metal environment from a hepta-coordinate high spin state to a hexa-coordinate low spin state.