Analogies of phonon anomalies and electronic gap features in the infrared response of Sr14-xCaxCu24O41and underdoped YBa2Cu3O6+x.

We present an experimental and theoretical study which compares the phonon anomalies and the electronic gap features in the infrared response of the weakly coupled two-leg-ladders in Sr14-xCaxCu24O41(SCCO) with those of the underdoped high-Tcsuperconductor YBa2Cu3O6+x(YBCO) and thereby reveals some surprising analogies. Specifically, we present a phenomenological model that describes the anomalous doping- and temperature-dependence of some of the phonon features in thea-axis response (field along the rungs of the ladders) of SCCO. It assumes that the phonons are coupled to charge oscillations within the ladders. Their changes with decreasing temperature reveal the formation of a crystal (density wave) of hole pairs that are oriented along the rungs. We also discuss the analogy to a similar model that was previously used to explain the phonon anomalies and an electronic plasma mode in thec-axis response (field perpendicular to the CuO2planes) of YBCO. We further confirm that an insulator-like pseudogap develops in thea-axis conductivity of SCCO which closely resembles that in thec-axis conductivity of YBCO. Most surprisingly, we find that thec-axis conductivity (field along the legs of the ladders) of SCCO is strikingly similar to the in-plane one (field parallel to the CuO2planes) of YBCO. Notably, in both cases a dip feature develops in the normal state spectra that is connected with a spectral weight shift toward low frequencies and can thus be associated with precursor superconducting pairing correlations that are lacking macroscopic phase coherence. This SCCO-YBCO analogy indicates that collective degrees of freedom contribute to the low-energy response of underdoped highTccuprates and it even suggests that the charges in the CuO2planes tend to segregate forming quasi-one-dimensional structures similar to the two-leg ladders, as predicted for the stripe-scenario or certain intertwinned states.

Field-dependent specific heat of the canonical underdoped cuprate superconductor [Formula: see text].

The cuprate superconductor [Formula: see text], in comparison with most other cuprates, has a stable stoichiometry, is largely free of defects and may be regarded as the canonical underdoped cuprate, displaying marked pseudogap behaviour and an associated distinct weakening of superconducting properties. This cuprate 'pseudogap' manifests as a partial gap in the electronic density of states at the Fermi level and is observed in most spectroscopic properties. After several decades of intensive study it is widely believed that the pseudogap closes, mean-field like, near a characteristic temperature, [Formula: see text], which rises with decreasing hole concentration, p. Here, we report extensive field-dependent electronic specific heat studies on [Formula: see text] up to an unprecedented 400 K and show unequivocally that the pseudogap never closes, remaining open to at least 400 K where [Formula: see text] is typically presumed to be about 150 K. We show from the NMR Knight shift and the electronic entropy that the Wilson ratio is numerically consistent with a weakly-interacting Fermion system for the near-nodal states. And, from the field-dependent specific heat, we characterise the impact of fluctuations and impurity scattering on the thermodynamic properties.

Pressure induced separation of phase-transition-triggered-abrupt vs. gradual components of spin crossover.

The application of pressure on [Co(II)(dpzca)2], which at ambient pressure undergoes abrupt spin crossover (SCO) with thermal hysteresis, gives unique insights into SCO. It reversibly separates the crystallographic phase transition (I41/a↔P21/c) and associated abrupt SCO from the underlying gradual SCO, as shown by detailed room temperature (RT) X-ray crystallography and temperature dependent magnetic susceptibility studies, both under a range of 10 different pressures. The pressure effects are shown to be reversible. The crystal structure of the pressure-induced low-spin state is determined at RT at 0.42(2) and 1.78(9) GPa. At the highest pressure [1.78(9) GPa] the Co-N bond lengths are consistent with the complex being fully LS, and the conjugated terdentate ligands are significantly distorted out of plane. The abrupt SCO event can be shifted up to RT by application of a hydrostatic pressure of ∼0.4 GPa. These magnetic susceptibility (vs. temperature) and X-ray crystallography (at RT) studies, under a range of pressures, show that the SCO can be tuned over a wide range of temperature and pressure space, including RT SCO.

Remarkable scan rate dependence for a highly constrained dinuclear iron(II) spin crossover complex with a wide thermal hysteresis loop.

The abrupt [HS-HS] ↔ localized [HS-LS] spin crossovers of a new triazole-based diiron(II) complex result in a record-equaling thermal hysteresis loop width for a dinuclear complex (ΔT = 22 K by SQUID magnetometer in "settle" mode) and show a remarkable scan rate dependence of only the cooling branch, as revealed by detailed magnetic, DSC, and Mössbauer studies.

Effect of N4-substituent choice on spin crossover in dinuclear iron(II) complexes of bis-terdentate 1,2,4-triazole-based ligands.

Seven new dinuclear iron(II) complexes of the general formula [Fe(II)2(PMRT)2](BF4)4·solvent, where PMRT is a 4-substituted-3,5-bis{[(2-pyridylmethyl)-amino]methyl}-4H-1,2,4-triazole, have been prepared in order to investigate the substituent effect on the spin crossover event. Variable temperature magnetic susceptibility and (57)Fe Mössbauer spectroscopy studies show that two of the complexes, [Fe(II)2(PMPT)2](BF4)4·H2O (N(4) substituent is pyrrolyl) and [Fe(II)2(PM(Ph)AT)2](BF4)4 (N(4) is N,N-diphenylamine), are stabilized in the [HS-HS] state between 300 and 2 K with weak antiferromagnetic interactions between the iron(II) centers. Five of the complexes showed gradual half spin crossover, from [HS-HS] to [HS-LS], with the following T(1/2) (K) values: 234 for [Fe(II)2(PMibT)2](BF4)4·3H2O (N(4) is isobutyl), 147 for [Fe(II)2(PMBzT)2](BF4)4 (N(4) is benzyl), 133 for [Fe(II)2(PM(CF3)PhT)2](BF4)4·DMF·H2O (N(4) is 3,5-bis(trifluoromethyl)phenyl), 187 for [Fe(II)2(PMPhT)2](BF4)4 (N(4) is phenyl), and 224 for [Fe(II)2(PMC16T)2](BF4)4 (N(4) is hexadecyl). Structure determinations carried out for three complexes, [Fe(II)2(PMPT)2](BF4)4·4DMF, [Fe(II)2(PMBzT)2](BF4)4·CH3CN, and [Fe(II)2(PM(Ph)AT)2](BF4)4·solvent, revealed that in all three complexes both iron(II) centers are stabilized in the high spin state at 90 K. A general and reliable 4-step route to PMRT ligands is also detailed.

Tunable SERS using gold nanoaggregates on an elastomeric substrate.

We report on the self-assembly of colloidal gold nanoparticles on a stretchable, elastomeric membrane, and the use of this membrane as a base substrate for far-field confocal Raman measurements. Surface-enhanced Raman scattering (SERS) enhancement for such a substrate was estimated as 10(6) to 10(7). Atomic force microscopy has been used to study the changes in nanoparticle topography when the membrane is stretched. The homogeneous strain defined by average relative motion of nanoparticles is approximately half the macroscopically-applied biaxial strain. The SERS intensity was maximized when the membrane was at rest (i.e. without stretch), and reduced as stretching was increased. Our measurements are consistent with theoretical and numerical SERS enhancements for the interstitial gap between two spheres. The data indicate that the resting gap between the spheres is 11 nm or 16 nm, using two theoretical models. This work represents progress towards particularly facile sample fabrication and in situ tuning techniques for SERS.

Reversible switching of a cobalt complex by thermal, pressure, and electrochemical stimuli: abrupt, complete, hysteretic spin crossover.

Triply switchable [Co(II)(dpzca)(2)] shows an abrupt, reversible, and hysteretic spin crossover (T(1/2)↓ = 168 K, T(1/2)↑ = 179 K, and ΔT(1/2) = 11 K) between the high-spin (HS) and low-spin (LS) states of cobalt(II), both of which have been structurally characterized. The spin transition is also reversibly triggered by pressure changes. Moreover, in a third reversible switching mechanism for this complex, the magnetic properties can be switched between HS cobalt(II) and LS cobalt(III) by redox.

Effect of counteranion X on the spin crossover properties of a family of diiron(II) triazole complexes [Fe(II)2(PMAT)2](X)4.

Seven diiron(II) complexes, [Fe(II)(2)(PMAT)(2)](X)(4), varying only in the anion X, have been prepared, where PMAT is 4-amino-3,5-bis{[(2-pyridylmethyl)-amino]methyl}-4H-1,2,4-triazole and X = BF(4)(-) (1), Cl(-) (2), PF(6)(-) (3), SbF(6)(-) (4), CF(3)SO(3)(-) (5), B(PhF)(4)(-) (6), and C(16)H(33)SO(3)(-) (7). Most were isolated as solvates, and the microcrystalline ([3], [4]·2H(2)O, [5]·H(2)O, and [6]·½MeCN) or powder ([2]·4H(2)O, and [7]·2H(2)O) samples obtained were studied by variable-temperature magnetic susceptibility and Mössbauer methods. A structure determination on a crystal of [2]·2MeOH·H(2)O, revealed it to be a [LS-HS] mixed low spin (LS)-high spin (HS) state dinuclear complex at 90 K, but fully high spin, [HS-HS], at 293 K. In contrast, structures of both [5]·¾IPA·H(2)O and [7]·1.6MeOH·0.4H(2)O showed them to be [HS-HS] at 90 K, whereas magnetic and Mössbauer studies on [5]·H(2)O and [7]·2H(2)O revealed a different spin state, [LS-HS], at 90 K, presumably because of the difference in solvation. None of these complexes undergo thermal spin crossover (SCO) to the fully LS form, [LS-LS]. The PF(6)(-) and SbF(6)(-) complexes, 3 and [4]·2H(2)O, appear to be a mixture of [HS-LS] and [HS-HS] at low temperature, and undergo gradual SCO to [HS-HS] on warming. The CF(3)SO(3)(-) complex [5]·H(2)O undergoes gradual, partial SCO from [HS-LS] to a mixture of [HS-LS] and [HS-HS] at T(1/2) ≈ 180 K. The B(PhF)(4)(-) and C(16)H(33)SO(3)(-) complexes, [6]·(1)/(2)MeCN and [7]·2H(2)O, are approximately [LS-HS] at all temperatures, with an onset of gradual SCO with T(1/2) > 300 K.

When three is not a crowd: the first trinuclear complexes of N4-substituted-3,5-dipyridyl-1,2,4-triazole ligands, [Fe(II)3(Rdpt)4(NCS)6].

The first examples of trinuclear complexes of any dipyridyltriazole, [Fe(II)(3)(Rdpt)(4)(NCS)(6)], are, respectively: [HS-HS-HS] when Rdpt = phdpt and "[LS-HS-LS]" when Rdpt = ibdpt.

Room-temperature spin crossover and Langmuir-Blodgett film formation of an iron(II) triazole complex featuring a long alkyl chain substituent: the tail that wags the dog.

[Fe(II)(C(16)dpt)(2)(NCS)(2)].(2/3)H(2)O displays temperature-mediated spin crossover (SCO) with T((1/2)) = 290 K and the long alkyl chain substituent on the dipyridyltriazole ligand facilitates the formation of a stable Langmuir-Blodgett film at an air-water interface.

Synthesis and structure of Na+-intercalated WO3(4,4-bipyridyl)0.5.

WO3(4,4-bipyridyl)0.5 was doped with Na+ by ion implantation so as to alter the electronic structure. Single-crystal X-ray diffraction reveals layers of corner-shared WO5N octahedra linked by bipyridine. In the observed space group of Pbca, the fully-ordered bipyridyls form cages with Na+ disordered bimodally about the cage centre.

Spin crossover in co-crystallised 2 ratio 1 cisratiotrans [Fe(II)(pldpt)(2)(NCS)(2)] occurs only in (1/3) of the iron centres.

The first spin crossover (SCO) active sample of co-crystallised stereoisomers (cisratiotrans, 2 ratio 1) is fully high spin (HS) at room temperature but displays temperature mediated SCO in which only a third of the iron(ii) centres change spin state.