A.D. Naik

Insights into the Origin of Cooperative Effects in the Spin Transition of [Fe(NH2trz)3](NO3)2: the Role of Supramolecular Interactions Evidenced in the Crystal Structure of [Cu(NH2trz)3](NO3)2·H2O

The thermally induced hysteretic spin transition (ST) that occurs in the polymeric chain compound [Fe(NH(2)trz)(3)](NO(3))(2) (1) above room temperature (T(c)(upward arrow) = 347 K, T(c)(downward arrow) = 314 K) has been tracked by (57)Fe Mössbauer spectroscopy, SQUID magnetometry, differential scanning calorimetry (DSC), and X-ray powder diffraction (XPRD) at variable temperatures. From the XRPD pattern indexation, an orthorhombic primitive cell was observed with the following cell parameters: a = 11.83(2) A, b = 9.72(1) A, c = 6.361(9) A at 298 K (low-spin state) and a = 14.37(2) A, b = 9.61(4) A, c = 6.76(4) A at 380 K (high-spin state). The enthalpy and entropy variation associated to the ST of 1, have been evaluated by DSC as DeltaH = 23(1) kJ mol(-1) and DeltaS = 69.6(1) J mol(-1) K(-1). These thermodynamic data were used within a two-level Ising like model for the statistical analysis of First Order Reversal Curve (FORC) diagram that was recorded for 1, in the cooling mode. Strong intramolecular cooperative effects are witnessed by the derived interaction parameter of J = 496 K. The crystal structure of [Cu(NH(2)trz)(3)](NO(3))(2).H(2)O (2) was obtained thanks to high quality single crystals prepared by slow evaporation after hydrothermal pretreatment. The catena poly[mu-tris(4-amino-1,2,4-triazole-N1,N2) copper(II)] dinitrate monohydrate (2) crystallizes in the monoclinic space group C2/c, with a = 16.635(6) A, b = 13.223(4) A, c = 7.805(3) A, beta = 102.56(3) degrees, Z = 4. Complex 2 is a 1D infinite chain containing triple N1,N2-1,2,4-triazole bridges with an intra-chain distance of Cu...Cu = 3.903(1) A. A dense H-bonding network with the nitrate counteranion involved in intra-chain and inter-chain interactions is observed. Such a supramolecular network could be at the origin of the unusually large hysteresis loop displayed by 1 (DeltaT approximately 33 K), as a result of an efficient propagation of elastic interactions through the network. This hypothesis is strengthened by the crystal structure of 2 and by the absence of crystallographic phase transition for 1 over the whole temperature range of investigation as shown by XRPD.

Spin Transition Charted in a Fluorophore-Tagged Thermochromic Dinuclear Iron(II) Complex

The first crystal structures of a dinuclear iron(II) complex with three N1,N2-1,2,4-triazole bridges in the high-spin and low-spin states are reported. Its sharp spin transition, which was probed using X-ray, calorimetric, magnetic, and (57)Fe Mossbauer analyses, is also delineated in the crystalline state by variable-temperature fluorimetry for the first time.

Insights into the Origin of Solid-State Photochromism and Thermochromism of N-Salicylideneanils: The Intriguing Case of Aminopyridines.

The relationships between the crystal structure and optical properties of switchable N-salicylideneanils have been revised and discussed on the basis of new experimental results and a computational approach. N-salicylidene-3-aminopyridine (L(3)) is a versatile thermo- and photochromic molecule. It also exhibits an infinitely slow thermal back relaxation (k = 9.9x10(-8) s(-1)) after photoswitching that is suitable for optical memories. Contrary to reports in the literature, N-salicylidene-4-aminopyridine (L(4)) is exclusively thermochromic. To explain these unexpected optical properties in the solid state, crystallography combined with UV-visible spectroscopic data was exploited. L(3) was also used as a ligand in new thermochromic coordination complexes [M(CH(3)OH)(2)(L(3))(2)(NCX)(2)], in which M(II) = Fe, Co, Ni, Cu or Mn and X = S or Se (1-6), which allowed the fine-tuning of the electron density in the photochromic moiety. The influence of the coordination through the nitrogen of the pyridine ring is also fully discussed.

A symmetry-breaking spin-state transition in iron(III)

Stepping up: A two-step magnetic spin transition with accompanying structural phase transitions is reported for the first time for Fe III. The transitions are observed at 187 K and 90 K on cooling with a hysteretic transition recorded upon heating during the first crossover at 106 K. The intermediate phase persists over 97 K and contains an unprecedented [HS-HS-LS] motif with tripling of the unit cell. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electronic and structural aspects of spin transitions observed by optical microscopy. The case of [Fe(ptz)6](BF4)2.

The colorimetric analysis of images recorded with an optical microscope during the onset of the spin crossover transformation allows monitoring separately the involved electronic and structural aspects, through the separation of resonant absorption and scattering effects. Complementary information can also be obtained by using the polarized modes of the microscope. These potentialities are illustrated by the observation of [Fe(ptz)(6)](BF(4))(2) single crystals during the onset of the thermal transitions in the 110-140 K range. We characterized the interplay between the electronic (HS <--> LS) and structural (order <--> disorder) transformations. Elastic stresses and mechanical effects (hopping, self-cleavage) generated by the volume change upon electronic transition are also illustrated, with their impact on the photoswitching properties of the crystals.

Selective and reusable iron(II)-based molecular sensor for the vapor-phase detection of alcohols

A mononuclear iron(II) neutral complex (1) is screened for sensing abilities for a wide spectrum of chemicals and to evaluate the response function toward physical perturbation like temperature and mechanical stress. Interestingly, 1 precisely detects methanol among an alcohol series. The sensing process is visually detectable, fatigue-resistant, highly selective, and reusable. The sensing ability is attributed to molecular sieving and subsequent spin-state change of iron centers, after a crystal-to-crystal transformation.

Cooperative Spin Transition in a Mononuclear Manganese(III) Complex

Mind the gap: A complete, cooperative spin transition for a mononuclear Mn(III) complex is reported with an 8 K hysteresis window. Raman spectra collected at a single temperature in warming and cooling modes confirm the electronic bistability within the hysteresis loop. The source of the cooperativity is a disconnection in the hydrogen-bonded 1D chains that connect adjacent cations owing to an order-disorder transition in the PF(6)(-) counterion.

FeII Spin Transition Materials Including an Amino–Ester 1,2,4-Triazole Derivative, Operating at, below, and above Room Temperature

A new family of one-dimensional Fe(II) 1,2,4-triazole spin transition coordination polymers for which a modification of anion and crystallization solvent can tune the switching temperature over a wide range, including the room temperature region, is reported. This series of materials was prepared as powders after reaction of ethyl-4H-1,2,4-triazol-4-yl-acetate (αEtGlytrz) with an iron salt from a MeOH/H2O medium affording: [Fe(αEtGlytrz)3](ClO4)2 (1); [Fe(αEtGlytrz)3](ClO4)2·CH3OH (2); [Fe(αEtGlytrz)3](NO3)2·H2O (3); [Fe(αEtGlytrz)3](NO3)2 (4); [Fe(αEtGlytrz)3](BF4)2·0.5H2O (5); [Fe(αEtGlytrz)3](BF4)2 (6); and [Fe(αEtGlytrz)3](CF3SO3)2·2H2O (7). Their spin transition properties were investigated by (57)Fe Mossbauer spectroscopy, superconducting quantum interference device (SQUID) magnetometry, and differential scanning calorimetry (DSC). The temperature dependence of the high-spin molar fraction derived from (57)Fe Mössbauer spectroscopy in 1 reveals an abrupt single step transition between low-spin and high-spin states with a hysteresis loop of width 5 K (Tc(↑) = 296 K and Tc(↓) = 291 K). The properties drastically change with modification of anion and/or lattice solvent. The transition temperatures, deduced by SQUID magnetometry, shift to Tc(↑) = 273 K and Tc(↓) = 263 K for (2), Tc(↑) = 353 K and Tc(↓) = 333 K for (3), Tc(↑) = 338 K and Tc(↓) = 278 K for (4), T(↑) = 320 K and T(↓) = 305 K for (5), Tc(↑) = 106 K and Tc(↓) = 92 K for (6), and T(↑) = 325 K and T(↓) = 322 K for (7). Annealing experiments of 3 lead to a change of the morphology, texture, and magnetic properties of the sample. A dehydration/rehydration process associated with a spin state change was analyzed by a mean-field macroscopic master equation using a two-level Hamiltonian Ising-like model for 3. A new structural-property relationship was also identified for this series of materials [Fe(αEtGlytrz)3](anion)2·nSolvent based on Mössbauer and DSC measurements. The entropy gap associated with the spin transition and the volume of the inserted counteranion shows a linear trend, with decrease in entropy with increasing the size of the counteranion. The first materials of this substance class to display a complete spin transition in both spin states are also presented.

Crystal engineering of Fe(II) spin crossover coordination polymers derived from triazole or tetrazole ligands.

The past decade has witnessed intense research activity in the area of Fe(II) spin crossover coordination polymers, which are structurally diverse and functionally intriguing materials. In this endeavor, a less exploited series of ligands have been selected among various N-donor triazole and tetrazole molecules. Developing conventions that allow the tailoring of such functional materials with predictable architecture and properties is an important objective and current interest in crystal engineering. However, detailed knowledge on the structure-property correlation is still scanty due to the small number of crystal structures of such compounds. The principal focus is to decipher the effect of various supramolecular factors such as intermolecular interactions, hydrogen bonding etc., on the resultant Fe(II) coordination polymers. This tutorial review aims at highlighting some of the developments of such structurally diverse and functionally intriguing 1D polymeric chains, 2D and 3D networks built from triazole or tetrazole ligands exhibiting fascinating spin crossover phenomena.

Single-walled metal-organic nanotube built from a simple synthon.

A conformationally flexible triazole-carboxylic acid ligand derived from an L-amino acid, namely, 4 H-1,2,4-triazol-4-yl-acetic acid (αHGlytrz), has been exploited to synthesize a structurally diverse and functionally intriguing metal-organic framework with CuSiF6. The crystal structure reveals a novel single-walled metal-organic nanotube (SWMONT), namely, {[Cu3(μ3-OH)(H2O)3(Glytrz)3]⋅SiF6⋅8 H2O⋅X}∞ (1), (where X = disordered lattice water molecules) having a pore size as large as zeolites. Compound 1 was synthesized as crystals, as powder, or as layers by precipitation/electrodeposition. Mercury intrusion porosimetry demonstrates the ability of this material to store metallic mercury, after a pressure treatment, contrary to previous literature examples.