Muon-spin-relaxation and bulk measurements of the magnetic-field penetration depth suggest that the cuprate high-7V, bismuthate, organic, Chevrel-phase, and heavy-fermion systems possibly belong to a unique group of superconductors characterized by high transition temperatures T c relative to the values of n s /m* (carrier density/effective mass). This feature distinguishes these exotic superconductors from ordinary BCS superconductors.
Ultrafast processes can now be studied with the combined atomic spatial resolution of diffraction methods and the temporal resolution of femtosecond optical spectroscopy by using femtosecond pulses of electrons or hard X-rays as structural probes. However, it is challenging to apply these methods to organic materials, which have weak scattering centres, thermal lability, and poor heat conduction. These characteristics mean that the source needs to be extremely bright to enable us to obtain high-quality diffraction data before cumulative heating effects from the laser excitation either degrade the sample or mask the structural dynamics. Here we show that a recently developed, ultrabright femtosecond electron source makes it possible to monitor the molecular motions in the organic salt (EDO-TTF)2PF6 as it undergoes its photo-induced insulator-to-metal phase transition. After the ultrafast laser excitation, we record time-delayed diffraction patterns that allow us to identify hundreds of Bragg reflections with which to map the structural evolution of the system. The data and supporting model calculations indicate the formation of a transient intermediate structure in the early stage of charge delocalization (less than five picoseconds), and reveal that the molecular motions driving its formation are distinct from those that, assisted by thermal relaxation, convert the system into a metallic state on the hundred-picosecond timescale. These findings establish the potential of ultrabright femtosecond electron sources for probing the primary processes governing structural dynamics with atomic resolution in labile systems relevant to chemistry and biology.
An ambient pressure superconductivity of (BEDT-TTF)2Cu(SCN)2 was observed by d.c. magnetic susceptibility and electrical conductivity measurements. The superconducting critical temperature is the highest (TC=10.4 K) among the organic superconductors so far obtained, even though the anion has a positional disorder in the crystal.
Radical anion salts of metal-containing and metal-free phthalocyanines [MPc(3-)](·-), where M = Cu(II), Ni(II), H2, Sn(II), Pb(II), Ti(IV)O, and V(IV)O (1-10) with tetraalkylammonium cations have been obtained as single crystals by phthalocyanine reduction with sodium fluorenone ketyl. Their formation is accompanied by the Pc ligand reduction and affects the molecular structure of metal phthalocyanine radical anions as well as their optical and magnetic properties. Radical anions are characterized by the alternation of short and long C-Nimine bonds in the Pc ligand owing to the disruption of its aromaticity. Salts 1-10 show new bands at 833-1041 nm in the NIR range, whereas the Q- and Soret bands are blue-shifted by 0.13-0.25 eV (38-92 nm) and 0.04-0.07 eV (4-13 nm), respectively. Radical anions with Ni(II), Sn(II), Pb(II), and Ti(IV)O have S = 1/2 spin state, whereas [Cu(II)Pc(3-)](·-) and [V(IV)OPc(3-)](·-) containing paramagnetic Cu(II) and V(IV)O have two S = 1/2 spins per radical anion. Central metal atoms strongly affect EPR spectra of phthalocyanine radical anions. Instead of narrow EPR signals characteristic of metal-free phthalocyanine radical anions [H2Pc(3-)](·-) (linewidth of 0.08-0.24 mT), broad EPR signals are manifested (linewidth of 2-70 mT) with g-factors and linewidths that are strongly temperature-dependent. Salt 11 containing the [Na(I)Pc(2-)](-) anions as well as previously studied [Fe(I)Pc(2-)](-) and [Co(I)Pc(2-)](-) anions that are formed without reduction of the Pc ligand do not show changes in molecular structure or optical and magnetic properties characteristic of [MPc(3-)](·-) in 1-10.
We report that the organic salt (EDO-TTF)2PF6 with 3/4-filled-band (1/4-filled in terms of holes), which forms an organic metal with strong electron and lattice correlation, shows a highly sensitive response to photoexcitation. An ultrafast, photoinduced phase transition from the insulator phase to the metal phase can be induced with very weak excitation intensity at near room temperature. This response makes the material attractive for applications in switching devices with room-temperature operation. The observed photo-induced spectroscopic change shows that this photoinduced phase transition process is caused by the cooperative melting of charge ordering assisted by coherent phonon generation.
The complex formation of
bis(ethylenedioxy)tetrathiafulvalene (BEDO-TTF) with 29
organic electron
acceptors and six organic anions yielded 37 charge-transfer (CT)
complexes, about three-quarters of which exhibited
metallic behavior. The BEDO-TTF molecule proves to be an excellent
source for stable metals irrespective of the
structure, shape, size, and electron affinity of counter components.
The crystal structure of metallic BEDO-TTF
complexes indicates a strong aggregation of donor molecules into a
two-dimensional (2D) layered structure by the
aid of both intermolecular CH···O and side-by-side heteroatom
contacts. Band calculations based on an extended
Hückel method demonstrate that the sulfur atoms of the BEDO-TTF
molecule are dominant for 2D intermolecular
overlap. The resulting 2D electronic bands with large band width
serve to stabilize the metallic state even at low
temperatures. A comparison between the structural properties of
complexes of BEDO-TTF and those of its sulfur
analog BEDT-TTF (BEDT-TTF =
bis(ethylenedithio)tetrathiafulvalene) demonstrates that the
oxygen atoms of the
BEDO-TTF molecule not only enhance the intermolecular S··S atomic
contacts due to its small size, but also determine
donor packing through multiple weak hydrogen bondings. The nicely
combined roles of these heteroatoms are the
origins of the strongly stabilized metallic state in BEDO-TTF complexes
without aid of heavier selenium and/or
further addition of sulfur atoms on TTF moiety.
The effects of pressure on a quantum spin liquid are investigated in an organic Mott insulator κ-(ET)_{2}Ag_{2}(CN)_{3} with a spin-1/2 triangular lattice. The application of negative chemical pressure to κ-(ET)_{2}Cu_{2}(CN)_{3}, which is a well-known sister Mott insulator, allows for extensive tuning of antiferromagnetic exchange coupling, with J/k_{B}=175-310 K, under hydrostatic pressure. Based on ^{13}C nuclear magnetic resonance measurements under pressure, we uncover universal scaling in the static and dynamic spin susceptibilities down to low temperatures ∼0.1k_{B}T/J. The persistent fluctuations and residual specific heat coefficient are consistent with the presence of gapless low-lying excitations. Our results thus demonstrate the fundamental finite-temperature properties of a quantum spin liquid in a wide parameter range.
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