Unusual triplet–triplet annihilation in a 3D copper(i) chloride coordination polymer

2019 ◽  
Vol 21 (30) ◽  
pp. 16538-16548 ◽  
Author(s):  
Adrien Schlachter ◽  
Antoine Bonnot ◽  
Daniel Fortin ◽  
Paul-Ludovic Karsenti ◽  
Michael Knorr ◽  
...  
Keyword(s):  
Coordination Polymer ◽  
Activation Barrier ◽  
Unit Cell ◽  
Large Contraction ◽  
Triplet Triplet Annihilation

[Cu2Cl2(EtS(CH2)4SEt)4]n exhibits ultrafast Dexter driven triplet–triplet annihilation at 298 K (kQ = 1.3 × 1010 s−1) but a significantly slower one at 77 K (by 20 folds), despite large contraction of the unit cell. This process is explained by a large activation barrier.

A Two-Dimensional Coordination Polymer Formed from Cobalt(II) and an Extended Dipyridyl Ligand

2020 ◽  
Vol 73 (6) ◽  
pp. 547 ◽  
Author(s):  
Hydar A. AL-Fayaad ◽  
Rashid G. Siddique ◽  
Kasun S. Athukorala Arachchige ◽  
Jack K. Clegg
Keyword(s):  
Coordination Polymer ◽  
Cell Volume ◽  
Crystal Structures ◽  
Unit Cell Volume ◽  
Suzuki Coupling ◽  
Unit Cell ◽  
Square Lattice ◽  
Two Dimensional ◽  
Cobalt Ions ◽  
One Dimensional

The synthesis of the extended dipyridyl ligand 4,4′-(2,5-dimethyl-1,4-phenylene)dipyridine (L) in an improved yield via the palladium catalysed Suzuki coupling of 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine (1) and 1,4-dibromo-2,5-dimethylbenzene (2) is reported along with its use to form a two-dimensional coordination polymer [Co2L2(OAc)4(H2O)2]n. The coordination polymer consists of one-dimensional chains of octahedral cobalt ions bridged by acetate ligands which are connected to form two dimensional sheets with square lattice (sql) topology via the dipyridyl ligands (L). The structure contains small voids totalling ~6.6% of the unit cell volume. The crystal structures 1, L, L·2H2O, and L·2HNO3 are also reported.

Anisotropic compressibility of the coordination polymer emim[Mn(btc)]

2016 ◽  
Vol 72 (3) ◽  
pp. 389-394 ◽  
Author(s):  
Solveig R. Madsen ◽  
Stephen A. Moggach ◽  
Jacob Overgaard ◽  
Bo Brummerstedt Iversen
Keyword(s):  
Coordination Polymer ◽  
Unit Cell ◽  
Ambient Conditions ◽  
X Ray Diffraction ◽  
Imidazolium Cation ◽  
Carboxylate Ligands ◽  
Strain Gradients ◽  
Coordination Environment ◽  
X Ray ◽  
Hydrostatic Limit

The effect of pressure on the crystal structure of a coordination polymer, emim[MnII(btc)] (emim = 1-ethyl,3-methyl imidazolium cation, btc = 1,3,5-benzene-tricarboxylate), was investigated with single-crystal X-ray diffraction. At 4.3 GPa the unit-cell volume had decreased by 14% compared with ambient conditions. The unit-cell contraction is highly anisotropic, with thea- andb-axes decreasing by 5.5 and 9.5%, respectively, and thec-axis compressing a mere 0.25% up to 1.7 GPa followed by a 0.2% expansion between 1.7 and 4.3 GPa. The 0.2% increase in length of thec-axis in this interval happens above the quasi-hydrostatic limit of the pressure-transmitting medium and therefore it might be a consequence of strain gradients. Under ambient conditions, two MnO6units are connected by two carboxylate ligands to form dimeric units. On increasing pressure, a non-bonded O atom from a bridging carboxylate group approaches the Mn atom, with the Mn—O distance decreasing from 2.866 (1) Å at 0.3 GPa to 2.482 (6) Å at 4.3 GPa, increasing the coordination environment of the Mn ion from six- to seven-coordinated.

The 3D [(Cu2Br2){μ-EtS(CH2)4SEt}]n material: a rare example of a coordination polymer exhibiting triplet–triplet annihilation

2016 ◽  
Vol 18 (36) ◽  
pp. 24845-24849 ◽  
Author(s):  
Antoine Bonnot ◽  
Paul-Ludovic Karsenti ◽  
Frank Juvenal ◽  
Christopher Golz ◽  
Carsten Strohmann ◽  
...  
Keyword(s):  
Coordination Polymer ◽  
Excitation Energy ◽  
Rare Case ◽  
Inorganic Material ◽  
Energy Migration ◽  
Triplet Triplet Annihilation

A very rare case of excitation energy migration has been observed for an inorganic material.

Novel Zn(II) coordination polymer based on 1,2-bis(4-pyridyl)hydrazine — From two-dimensional to three-dimensional network

2012 ◽  
Vol 90 (1) ◽  
pp. 100-107 ◽  
Author(s):  
Huaishan Wang ◽  
Lap Szeto ◽  
Wesley Ting Kwok Chan ◽  
Ho-Lun Yeung ◽  
Ka-Leung Wong ◽  
...  
Keyword(s):  
Coordination Polymer ◽  
Terephthalic Acid ◽  
Three Dimensional ◽  
Unit Cell ◽  
Two Dimensional ◽  
Dimensional Network

Two MOFs were reported based on Zn(II) with 1,2-bis(4-pyridyl)hydrazine (L1); a two-dimensional interpenetrating MOF I of formula [Zn2(L1)2(L2)2]∞ was formed with terephthalic acid (L2) as an additional linker. A three-dimensional MOF II of formula [Zn2(L1)2(L3)2]∞, was formed with the use of a larger spacer 2,6-naphthalenedicarboxylic acid (L3). MOF II consists of large porosity with a total volume of 3746 Å3 that occupies 34.1% of the unit cell.

High-resolution structure determination by ALCHEMI

1983 ◽  
Vol 41 ◽  
pp. 178-181 ◽  
Author(s):  
Peter G. Self ◽  
Peter R. Buseck
Keyword(s):  
Site Occupancy ◽  
Real Space ◽  
Unit Cell ◽  
Bragg Angle ◽  
Electron Current ◽  
High Resolution Structure ◽  
Beam Incident ◽  
Crystallographic Planes ◽  
Electron Beam Incident ◽  
Resolution Structure

ALCHEMI (Atom Location by CHanneling Enhanced Microanalysis) enables the site occupancy of atoms in single crystals to be determined. In this article the fundamentals of the method for both EDS and EELS will be discussed. Unlike HRTEM, ALCHEMI does not place stringent resolution requirements on the microscope and, because EDS clearly distinguishes between elements of similar atomic number, it can offer some advantages over HRTEM. It does however, place certain constraints on the crystal. These constraints are: a) the sites of interest must lie on alternate crystallographic planes, b) the projected charge density on the alternate planes must be significantly different, and c) there must be at least one atomic species that lies solely on one of the planes.An electron beam incident on a crystal undergoes elastic scattering; in reciprocal space this is seen as a diffraction pattern and in real space this is a modulation of the electron current across the unit cell. When diffraction is strong (i.e., when the crystal is oriented near to the Bragg angle of a low-order reflection) the electron current at one point in the unit cell will differ significantly from that at another point.

The External Shape of Human γ GI Immunoglobulin from Crystal Sections

1971 ◽  
Vol 29 ◽  
pp. 428-429
Author(s):  
L. W. Labaw
Keyword(s):  
Molecular Weight ◽  
Sodium Phosphate ◽  
Osmium Tetroxide ◽  
Unit Cell ◽  
Monoclinic Space Group ◽  
X Ray ◽  
Large Molecular Weight ◽  
Cell Dimensions ◽  
Unit Cell Dimensions ◽  
Crystallographic Axes

Crystals of a human γGl immunoglobulin have the external morphology of diamond shaped prisms. X-ray studies have shown them to be monoclinic, space group C2, with 2 molecules per unit cell. The unit cell dimensions are a = 194.1, b = 91.7, c = 51.6Å, 8 = 102°. The relatively large molecular weight of 151,000 and these unit cell dimensions made this a promising crystal to study in the EM.Crystals similar to those used in the x-ray studies were fixed at 5°C for three weeks in a solution of mother liquor containing 5 x 10-5M sodium phosphate, pH 7.0, and 0.03% glutaraldehyde. They were postfixed with 1% osmium tetroxide for 15 min. and embedded in Maraglas the usual way. Sections were cut perpendicular to the three crystallographic axes. Such a section cut with its plane perpendicular to the z direction is shown in Fig. 1.This projection of the crystal in the z direction shows periodicities in at least four different directions but these are only seen clearly by sighting obliquely along the micrograph.

The orientation of sickle hemoglobin fibers within fascicles

1988 ◽  
Vol 46 ◽  
pp. 400-401
Author(s):  
Christopher A. Miller ◽  
Bridget Carragher ◽  
William A. McDade ◽  
Robert Josephs
Keyword(s):  
Sickle Cell ◽  
Sickle Cell Anemia ◽  
Relative Orientation ◽  
Unit Cell ◽  
Red Cell ◽  
High Ph ◽  
Sickle Hemoglobin ◽  
Polar Crystal ◽  
Helical Configuration

Highly ordered bundles of deoxyhemoglobin S (HbS) fibers, termed fascicles, are intermediates in the high pH crystallization pathway of HbS. These fibers consist of 7 Wishner-Love double strands in a helical configuration. Since each double strand has a polarity, the odd number of double strands in the fiber imparts a net polarity to the structure. HbS crystals have a unit cell containing two double strands, one of each polarity, resulting in a net polarity of zero. Therefore a rearrangement of the double strands must occur to form a non-polar crystal from the polar fibers. To determine the role of fascicles as an intermediate in the crystallization pathway it is important to understand the relative orientation of fibers within fascicles. Furthermore, an understanding of fascicle structure may have implications for the design of potential sickling inhibitors, since it is bundles of fibers which cause the red cell distortion responsible for the vaso-occlusive complications characteristic of sickle cell anemia.

Kinematical and Dynamical CBED Pattern Models: Increasing the Accuracy of the Unit-Cell Parameter Measurements Based on CBED Patterns

1990 ◽  
Vol 48 (2) ◽  
pp. 540-541
Author(s):  
I.N. Yadhikov ◽  
S.K. Maksimov
Keyword(s):  
Reciprocal Lattice ◽  
Unit Cell ◽  
Reciprocal Lattice Vector ◽  
Unit Cell Parameters ◽  
Lattice Vector ◽  
Cell Parameters ◽  
Accuracy Of Measurements ◽  
The Difference ◽  
Image Position ◽  
Convergent Beam

Convergent beam electron diffraction (CBED) is widely used as a microanalysis tool. By the relative position of HOLZ-lines (Higher Order Laue Zone) in CBED-patterns one can determine the unit cell parameters with a high accuracy up to 0.1%. For this purpose, maps of HOLZ-lines are simulated with the help of a computer so that the best matching of maps with experimental CBED-pattern should be reached. In maps, HOLZ-lines are approximated, as a rule, by straight lines. The actual HOLZ-lines, however, are different from the straights. If we decrease accelerating voltage, the difference is increased and, thus, the accuracy of the unit cell parameters determination by the method becomes lower.To improve the accuracy of measurements it is necessary to give up the HOLZ-lines substitution by the straights. According to the kinematical theory a HOLZ-line is merely a fragment of ellipse arc described by the parametric equationwith arc corresponding to change of β parameter from -90° to +90°, wherevector, h - the distance between Laue zones, g - the value of the reciprocal lattice vector, g‖ - the value of the reciprocal lattice vector projection on zero Laue zone.

Structure Information From Electron Diffraction Intensities

1990 ◽  
Vol 48 (2) ◽  
pp. 516-517
Author(s):  
J. Gjønnes ◽  
N. Bøe ◽  
K. Gjønnes
Keyword(s):  
Computational Effort ◽  
Unit Cell ◽  
Small Unit ◽  
Structure Information ◽  
Dispersion Surface ◽  
Integrated Intensity ◽  
The One ◽  
Image Position ◽  
Convergent Beam ◽  
Beam Patterns

Structure information of high precision can be extracted from intentsity details in convergent beam patterns like the one reproduced in Fig 1. From low order reflections for small unit cell crystals,bonding charges, ionicities and atomic parameters can be derived, (Zuo, Spence and O’Keefe, 1988; Zuo, Spence and Høier 1989; Gjønnes, Matsuhata and Taftø, 1989) , but extension to larger unit cell ma seem difficult. The disks must then be reduced in order to avoid overlap calculations will become more complex and intensity features often less distinct Several avenues may be then explored: increased computational effort in order to handle the necessary many-parameter dynamical calculations; use of zone axis intensities at symmetry positions within the CBED disks, as in Figure 2 measurement of integrated intensity across K-line segments. In the last case measurable quantities which are well defined also from a theoretical viewpoint can be related to a two-beam like expression for the intensity profile:With as an effective Fourier potential equated to a gap at the dispersion surface, this intensity can be integrated across the line, with kinematical and dynamical limits proportional to and at low and high thickness respctively (Blackman, 1939).

The crystal structure of eugaAl

1992 ◽  
Vol 50 (2) ◽  
pp. 1452-1453
Author(s):  
H. Brigitte Krause ◽  
Yonglin Qian
Keyword(s):  
Crystal Structure ◽  
Electron Microscope ◽  
Zone Axis ◽  
Unit Cell ◽  
Polycrystalline Specimen ◽  
Lattice Constants

A polycrystalline specimen of nominal formula EuGaAl with unknown crystal structure was investigated by various electron microscope techniques; EDS-, SED-, and CBED data were taken on a Philips 400 electron microscope operated at 100kV, HREM data on a Hitachi 9000 microscope operated at 300kV. The EDS data confirmed the composition for the bulk of the material but, in addition, revealed particles with other fractions of the elements. Only the EuGaAl particles were further investigated. The unit cell was determined to be orthorhombic with a ratio: a/b=0.969(2) , a/c=0.234(2) and b/c=0.234(2). The lattice constants are a=4.54(5)Ȧ, b=4.68Ȧ and c=19.97(20)Ȧ. Based on systematic extinctions for hkl reflections with h+l=2n+l, the unit cell was found to be b-centered. CBED patterns of the [001], [100], and [010] zone axes are shown in Fig. 1. The zone axis patterns are in agreement with the above stated data except for diffused (2m+l,2n+l,0)- reflections, not compatible with the above stated systematic absences. But these occurred only occasionally in conjunction with a complicated noncommensurate superlattice pattern.

Sign in / Sign up

Export Citation Format

Share Document