2,262 research outputs found
Molybdenum complexes derived from the oxydianiline [(2-NH₂C₆H₄)₂O] : synthesis, characterization and ε-caprolactone ROP capability
The reaction of Na₂MoO₄ with 2,2′-oxydianiline (2-aminophenylether), (2-NH₂C₆H₄)₂O, LH₄, in DME (DME = 1,2-dimethoxyethane) in the presence of Et₃N and Me₃SiCl afforded either the bis(imido) molybdenum(VI) complex {Mo(L)Cl₂(DME)} (1), where L = (2-NC₆H₄)₂O, or the molybdenum(V) salt [Mo(L′)Cl₄][Et₃NH] (2), where L′ = [(2-NH₂C₆H₄)(2-NC₆H₄)O], depending on the work-up method employed. The same diamine reacted with in situ [Mo(NtBu)₂Cl₂(DME)] afforded a tetra-nuclear complex [Mo₄Cl₃(NtBu)₃(OSiMe₃)(μ₄-O)(L)₂(L′)₂]·2MeCN (3·2MeCN). The crystal structures of 1, 2 and 3·2MeCN have been determined. The structure of the bis(imido) complex 1 contains two unique molecules paired up via weak π-stacking, whereas the structure of 2 contains a chelating amine/imido ligand, and is made up of discrete units of two cations and two anions which are interacting via H-bonding. The tetra-nuclear structure 3 contains four different types of distorted octahedral molybdenum centre, and a bent Me₃SiO group thought to originate from the precursor synthesis. Complexes 1–3 have been screened for their ability to ring open polymerize (ROP) ε-caprolactone. For 1 and 3 (not 2), conversion rates were good (>90%) at high temperatures (100 °C) over 6–24 h, and the polymerization proceeded in a living manner
Manganese coordination chemistry of bis(imino)phenoxide derived [2 + 2] Schiff-base macrocyclic ligands
The [2 + 2] Schiff base macrocycles [2,2'-(CH₂CH₂)(C₆H₄N)₂-2,6-(4-RC₆H₃OH)]₂ (IʳH₂), upon reaction with MnCl₂ (two equivalents) afforded the bimetallic complex [Cl₃Mn(NCMe)][MnCl(IᵗᵇᵘH₂)] (2). Under similar conditions, use of the related [2 + 2] oxy-bridged macrocycle [2,2'-O(C₆H₄N=CH)₂4-RC₆H₃OH] (IIʳH₂), afforded the bimetallic complexes [(MnCl)₂IIʳ] (R = Me 3, tBu 4), whilst the macrocycle derived from 1,2-diaminobenzene and 5,5'-di-tert-butyl-2,2'-dihydroxy-3,3'-methylenedibenzaldehyde (IIIH₄) afforded the complex [(MnCl)₂(III)]·2MeCN (5·2MeCN). For comparative studies, the salt complexes [2,6-(ArNHCH)₂-4-MeC₆H₂O][MnCl₃(NCMe)] (Ar = 2,4-Me₂C₆H₃, 6) and {[2,6-(ArNHCH)₂-4-MeC₆H₂O][MnCl}₂[MnCl₄]·8CH₂Cl₂ (Ar = 4-MeC₆H₄, 7·8CH₂Cl₂) were prepared. The crystal structures of 1 - 7 are reported (synchrotron radiation was necessary for complexes 1, 3 and 5). Complexes 1 - 7 (not 5) were screened for their potential to act as pre-catalysts for the ring opening polymerization (ROP) of ε-caprolactone; 3, 4 and 6, 7 were inactive, whilst 1 and 2 exhibited only poor activity low conversion (<15 %) at temperatures above 60 °C
Comment on ``Local dimer-adatom stacking fault structures from 3x3 to 13x13 along Si(111)-7x7 domain boundaries''
Zhao et al. [Phys.Rev.B 58, 13824 (1998)] depicted several atomic structures
of domain boundaries on a Si(111) surface and criticized the article by the
present author and the co-workers. I will point out that their criticism is
incorrect and their structure models have no consistency.Comment: 2 pages. Physical Review B, to appea
Titanium additions to MgB2 conductors
A series of doping experiments are reported for MgB2 conductors that have
been synthesized using doped boron fibers prepared by chemical vapor
deposition(CVD) methods. Undoped MgB2 samples prepared from CVD prepared fibers
consistently give critical current densities, Jc, in the range of 500,000
A/cm^2 in low field at 5K. These values fall by a factor of about 100 as the
magnetic field increases to 3T. For heavily Ti-doped boron fibers where the
B/Ti ratio is comparable to 1, there is a substantial suppression of both Tc,
superconducting volume fraction, and Jc values. If, however, a sample with a
few percent Ti in B is deposited on a carbon coated SiC substrate and reacted
at 1100 degrees C for 15 min, then Tc is suppressed only a couple of degrees
Kelvin and critical current densities are found to be approximately 2-5 x 10^6
A/cm^2 for superconducting layers ranging from 4-10 micrometers thick. These
materials show Jc values over 10,000 A/cm^2 at 25K and 1.3 T.Comment: 10 pages, 6 figure
Superconductivity in MgB_2 doped with Ti and C
Measurements of the superconducting upper critical field, H_{c2}, and
critical current density, J_c, have been carried out for MgB_2 doped with Ti
and/or C in order to explore the problems encountered if these dopants are used
to enhance the superconducting performance. Carbon replaces boron in the MgB_2
lattice and apparently shortens the electronic mean free path thereby raising
H_c2. Titanium forms precipitates of either TiB or TiB_2 that enhance the flux
pinning and raise J_c. Most of these precipitates are intra-granular in the
MgB_2 phase. If approximately 0.5% Ti and approximately 2% C are co-deposited
with B to form doped boron fibers and these fibers are in turn reacted in Mg
vapor to form MgB_2, the resulting superconductor has H_{c2}(T=0) ~ 25 T and
J_c ~ 10,000 A/cm**2 at 5 K and 2.2 T.Comment: 11 pages, 10 figure
Isotope effects and possible pairing mechanism in optimally doped cuprate superconductors
We have studied the oxygen-isotope effects on T_{c} and in-plane penetration
depth \lambda_{ab}(0) in an optimally doped 3-layer cuprate
Bi_{1.6}Pb_{0.4}Sr_{2}Ca_{2}Cu_{3}O_{10+y} (T_{c} \sim 107 K). We find a small
oxygen-isotope effect on T_{c} (\alpha_{O} = 0.019), and a substantial effect
on \lambda_{ab} (0) (\Delta \lambda_{ab} (0)/\lambda_{ab} (0) = 2.5\pm0.5%).
The present results along with the previously observed isotope effects in
single-layer and double-layer cuprates indicate that the isotope exponent
\alpha_{O} in optimally doped cuprates is small while the isotope effect on the
in-plane effective supercarrier mass is substantial and nearly independent of
the number of the CuO_{2} layers. A plausible pairing mechanism is proposed to
explain the isotope effects, high-T_{c} superconductivity and tunneling spectra
in a consistent way.Comment: 5 pages, 4 figure
Low-cost, smartphone-based instant three-dimensional registration system for infant functional near-infrared spectroscopy applications
Significance
To effectively apply functional near-infrared spectroscopy (fNIRS)/diffuse optical tomography (DOT) devices, a three-dimensional (3D) model of the position of each optode on a subject’s scalp and the positions of that subject’s cranial landmarks are critical. Obtaining this information accurately in infants, who rarely stop moving, is an ongoing challenge.
Aim
We propose a smartphone-based registration system that can potentially achieve a full-head 3D scan of a 6-month-old infant instantly.
Approach
The proposed system is remotely controlled by a custom-designed Bluetooth controller. The scanned images can either be manually or automatically aligned to generate a 3D head surface model.
Results
A full-head 3D scan of a 6-month-old infant can be achieved within 2 s via this system. In testing on a realistic but static infant head model, the average Euclidean error of optode position using this device was 1.8 mm.
Conclusions
This low-cost 3D registration system therefore has the potential to permit accurate and near-instant fNIRS/DOT spatial registration
Molybdocalix[4]arene N,O-Schiff-base ligands
The ‘one-pot’ reaction of 2-hydroxy-3,5-di-tert-butylsalicylaldehyde with in situ generated ‘amino calixarene’ (from {Mo[(2-NC 6 H 4 ) 2 CH 2 CH 2 ]Cl 2 (DME)}, KOtBu and p-tert-butylcalix[4]areneH 4 LH 4 ) afforded, after work-up, the heterobimetallic salt K(NCMe) 2 [Mo(NCMe)(OEt)(2-C 6 H 4 CH 2 CH 2 C 6 H 4 NH 2 -2)L] (1∙2MeCN). By constrast, use of the ‘amino calixarene’ [Mo(NCMe)(2-C 6 H 4 CH 2 CH 2 C 6 H 4 NH 2 -2)L] afforded the potassium/ethoxide-free complex [Mo(NCMe)(2-C 6 H 4 CH 2 CH 2 C 6 H 4 N-2-CHC 6 H 2 -2′-(OH)-3′,5′-tBu)L] (2∙2MeCN). Reaction of the ‘amino calixarene’ (two equivalents) with the dialdehyde [1,3-(CHO) 2 -5-MeC 6 H 3 OH-2] led, following work-up, to the isolation of the cation-anion pair [C 46 H 42 N 4 O 2 ] 2+ [Mo 6 O 19 ] 2− ·C 2 H 3 N (3∙MeCN). The molecular structures of 1·2MeCN, 2·2MeCN and 3·MeCN are reported, for which it was necessary to use synchrotron radiation for data collection. Complex 1 contains an eliptical calixarene conformation as a result of π-interactions between the K + and the arene groups and a distorted O 5 N octahedral geometry at the molybdenum centre, whereas in ‘K + /ethoxide-free’ 2, the calixarene retains the cone conformation and the metal possesses a distorted octahedral O 4 N 2 coordination environment. In 3, a protonated macrocyclic cation, formed via hydrolysis, has weak intermolecular interactions with the polyoxomolybdate anion
Organoaluminium complexes derived from Anilines or Schiff bases for ring opening polymerization of epsilon-caprolactone, delta-valerolactone and rac-lactide
Reaction of R¹R²CHN=CH(3,5-tBu₂C₆H₂-OH-2) (R¹ = R² = Me L¹H; R¹ = Me, R² = Ph L²H; R¹ = R2 = Ph L³H) with one equivalent of R³3Al (R³ = Me, Et) afforded [(L¹-³)AlR³₂] (L¹, R³ = Me 1, R³ = Et 2; L², R³ = Me 3, R³ = Et 4; L³ R³ = Me 5, R³ = Et 6); complex 1 has been previously reported. Use of the N,O-ligand derived from 2,2/-diphenylglycine afforded either 5 or a by-product [Ph₂NCH₂(3,5-tBu₂C₆H₂-O-2)AlMe₂] (7). The known Schiff base complex [2-Ph₂PC₆H4CH₂(3,5-tBu₂C₃H₂-O-2)AlMe₂] (8) and the product of the reaction of 2-diphenylphosphinoaniline 1-NH₂,2-PPh₂C₆H4 with Me3Al, namely {Ph₂PC₆H4N[(Me₂Al)₂mu-Me](mu-Me₂Al)} (9) were also isolated. For structural and catalytic comparisons, complexes resulting from interaction of Me₃Al with diphenylamine or benzhydrylamine, namely {Ph₂N[(Me₂Al)2mu-Me]} (10) and [Ph₂CHNH(mu-Me₂Al)]₂·MeCN (11), were prepared. The molecular structures of the Schiff pro-ligands derived from Ph₂CHNH₂ and 2,2/-Ph2C(CO₂H)(NH₂), together with complexes 5, 7 and 9 - 11·MeCN were determined. All complexes have been screened for their ability to ring opening polymerization (ROP) epsilon-caprolactone, delta-valerolactone or rac-lactide, in the presence of benzyl alcohol, with or without solvent present. The co-polymerization of epsilon-caprolactone with rac-lactide has also been studied
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