scholarly journals Functionalized Tris(anilido)triazacyclononanes as Hexadentate Ligands for the Encapsulation of U(III), U(IV) and La(III) Cations

Inorganics ◽  
2021 ◽  
Vol 9 (12) ◽  
pp. 86
Author(s):  
Alasdair Formanuik ◽  
Fabrizio Ortu ◽  
Iñigo J. Vitorica-Yrezabal ◽  
Floriana Tuna ◽  
Eric J. L. McInnes ◽  
...  
Keyword(s):  
Solid State ◽  
Magnetic Measurements ◽  
Nir Spectroscopy ◽  
Small Molecule Activation ◽  
Electronic Effects ◽  
X Ray Diffraction ◽  
Aromatic Rings ◽  
A Minor ◽  
Solid State Structures ◽  
Group 1

Tripodal multidentate ligands have become increasingly popular in f-element chemistry for stabilizing unusual bonding motifs and supporting small molecule activation processes. The steric and electronic effects of ligand donor atom substituents have proved crucial in both of these applications. In this study we functionalized the previously reported tris-anilide ligand {tacn(SiMe2NPh)3} (tacn = 1,3,7-triazacyclononane) to incorporate substituted aromatic rings, with the aim of modifying f-element complex solubility and ligand steric effects. We report the synthesis of two proligands, {tacn(SiMe2NHAr)3} (Ar = C6H3Me2-3,5 or C6H4Me-4), and their respective group 1 transfer agents—{tacn(SiMe2NKAr)3}, M(III) complexes [M{tacn(SiMe2NAr)3}] for M = La and U, and U(IV) complexes [M{tacn(SiMe2NAr)3}(Cl)]. These compounds were characterized by multinuclear NMR and FTIR spectroscopy and elemental analysis. The paramagnetic uranium complexes were also characterized by solid state magnetic measurements and UV/Vis/NIR spectroscopy. U(III) complexes were additionally studied by EPR spectroscopy. The solid state structures of all f-block complexes were authenticated by single-crystal X-ray diffraction (XRD), together with a minor byproduct [U{tacn(SiMe2NC6H4Me-4)3}(I)]. Comparisons of the characterization data of our f-element complexes with similar literature examples containing the {tacn(SiMe2NPh)3} ligand set showed minor changes in physicochemical properties resulting from the different aromatic ring substitution patterns we investigated.

scholarly journals Solid-State Structures and Photoluminescence of Lamellar Architectures of Cu(I) and Ag(I) Paddlewheel Clusters with Hydrogen-Bonded Polar Guests

Molecules ◽  
2021 ◽  
Vol 26 (21) ◽  
pp. 6731
Author(s):  
Haruki Inoue ◽  
Yuga Yamashita ◽  
Yoshiki Ozawa ◽  
Toshikazu Ono ◽  
Masaaki Abe
Keyword(s):  
Solid State ◽  
Diffuse Reflectance Spectroscopy ◽  
X Ray Diffraction ◽  
Uv Illumination ◽  
Near Ir ◽  
Carboxylic Groups ◽  
Dta Analysis ◽  
Non Covalent Interactions ◽  
Solid State Structures ◽  
Covalent Interactions

Two hexanuclear paddlewheel-like clusters appending six carboxylic-acid pendants have been isolated with the inclusion of polar solvent guests: [Cu6(Hmna)6]·7DMF (1·7DMF) and [Ag6(Hmna)6]·8DMSO (2·8DMSO), where H2mna = 2-mercaptonicotininc acid, DMF = N,N’-dimethylformamide, and DMSO = dimethyl sulfoxide. The solvated clusters, together with their fully desolvated forms 1 and 2, have been characterized by FTIR, UV–Vis diffuse reflectance spectroscopy, TG-DTA analysis, and DFT calculations. Crystal structures of two solvated clusters 1·7DMF and 2·8DMSO have been unambiguously determined by single-crystal X-ray diffraction analysis. Six carboxylic groups appended on the clusters trap solvent guests, DMF or DMSO, through H-bonds. As a result, alternately stacked lamellar architectures comprising of a paddlewheel cluster layer and H-bonded solvent layer are formed. Upon UV illumination (λex = 365 nm), the solvated hexasilver(I) cluster 2·8DMSO gives intense greenish-yellow photoluminescence in the solid state (λPL = 545 nm, ΦPL = 0.17 at 298 K), whereas the solvated hexacopper(I) cluster 1·7DMF displays PL in the near-IR region (λPL = 765 nm, ΦPL = 0.38 at 298 K). Upon complete desolvation, a substantial bleach in the PL intensity (ΦPL < 0.01) is observed. The desorption–sorption response was studied by the solid-state PL spectroscopy. Non-covalent interactions in the crystal including intermolecular H-bonds, CH···π interactions, and π···π stack were found to play decisive roles in the creation of the lamellar architectures, small-molecule trap-and-release behavior, and guest-induced luminescence enhancement.

scholarly journals Bis(dicarbollide) Complexes of Transition Metals as a Platform for Molecular Switches. Study of Complexation of 8,8′-Bis(methylsulfanyl) Derivatives of Cobalt and Iron Bis(dicarbollides)

Molecules ◽  
2020 ◽  
Vol 25 (23) ◽  
pp. 5745
Author(s):  
Sergey A. Anufriev ◽  
Sergey V. Timofeev ◽  
Alexei A. Anisimov ◽  
Kyrill Yu. Suponitsky ◽  
Igor B. Sivaev
Keyword(s):  
Solid State ◽  
Transition Metal ◽  
Molecular Switches ◽  
X Ray Diffraction ◽  
Chelate Complexes ◽  
X Ray ◽  
Complexes Of Transition Metals ◽  
Silver Palladium ◽  
Solid State Structures ◽  
Derivatives Of

Complexation of the 8,8′-bis(methylsulfanyl) derivatives of cobalt and iron bis(dicarbollides) [8,8′-(MeS)2-3,3′-M(1,2-C2B9H10)2]− (M = Co, Fe) with copper, silver, palladium and rhodium leads to the formation of the corresponding chelate complexes, which is accompanied by a transition from the transoid to the cisoid conformation of the bis(dicarbollide) complex. This transition is reversible and can be used in design of coordination-driven molecular switches based on transition metal bis(dicarbollide) complexes. The solid-state structures of {(Ph3P)ClPd[8,8′- (MeS)2-3,3′-Co(1,2-C2B9H10)2-κ2-S,S′]} and {(COD)Rh[8,8′-(MeS)2-3,3′-Co(1,2-C2B9H10)2-κ2-S,S′]} were determined by single crystal X-ray diffraction.

scholarly journals Exploring the Self-Assembled Tacticity in Aurophilic Polymeric Arrangements of Diphosphanegold(I) Fluorothiolates

Molecules ◽  
2019 ◽  
Vol 24 (23) ◽  
pp. 4422 ◽  
Author(s):  
Moreno-Alcántar ◽  
Salazar ◽  
Romo-Islas ◽  
Flores-Álamo ◽  
Torrens
Keyword(s):  
Solid State ◽  
Self Assembly ◽  
Structural Diversity ◽  
Supramolecular Structures ◽  
X Ray Diffraction ◽  
Ligand Effects ◽  
Rational Control ◽  
Solid State Structures ◽  
Further Development ◽  
Aurophilic Interactions

Despite the recurrence of aurophilic interactions in the solid-state structures of gold(I) compounds, its rational control, modulation, and application in the generation of functional supramolecular structures is an area that requires further development. The ligand effects over the aurophilic-based supramolecular structures need to be better understood. This paper presents the supramolecular structural diversity of a series of new 1,3-bis(diphenylphosphane)propane (dppp) gold(I) fluorinated thiolates with the general formula [Au2(SRF)2(μ-dppp)] (SRF = SC6F5 (1); SC6HF4-4 (2); SC6H3(CF3)2-3,5 (3); SC6H4CF3-2 (4); SC6H4CF3-4 (5); SC6H3F2-3,4 (6); SC6H3F2-3,5 (7); SC6H4F-2 (8); SC6H4F-3 (9); SC6H4F-4 (10)). These compounds were synthesized and characterized, and six of their solid-state crystalline structures were determined using single-crystal X-ray diffraction. In the crystalline arrangement, they form aurophilic-bridged polymers. In these systems, the changes in the fluorination patterns of the thiolate ligands tune the aurophilic-induced self-assembly of the compounds causing tacticity and chiral differentiation of the monomers. This is an example of the use of ligand effects on the tune of the supramolecular association of gold complexes.

Copper(II) Complexes of a Tripyridyl Ligand: Anion-Dependent Metallosupramolecular Structures

2013 ◽  
Vol 66 (11) ◽  
pp. 1447 ◽  
Author(s):  
James E. M. Lewis ◽  
James D. Crowley
Keyword(s):  
Mass Spectrometry ◽  
Solid State ◽  
Coordination Polymer ◽  
Elemental Analysis ◽  
Spectroscopic Properties ◽  
Nitrate Salt ◽  
X Ray Diffraction ◽  
X Ray ◽  
Salt Structure ◽  
Solid State Structures

A series of copper(ii) complexes of the ligand 2,6-bis(pyridin-3-ylethynyl)pyridine have been synthesised and characterised by 1H and DOSY NMR, IR and UV-Vis spectroscopies, mass spectrometry, elemental analysis and single crystal X-ray diffraction. In solution these systems display almost identical spectroscopic properties, however the solid state structures are shown to vary widely, depending upon the choice of anion. The tetrafluoroborate salt was revealed to be a discrete Cu2L4 cage-like helicate. The tosylate salt, whilst of the same Cu2L4 stoichiometry, was shown to be a coordination polymer. Finally the nitrate salt structure was observed to be a discrete Cu2L2 metallocycle.

Structural, dielectric and magnetic properties of Pr-, Tb- and Dy-doped (Bi0.95RE0.05)(Fe0.95Mn0.05)O3 ceramics synthesized by solid-state reaction method

2013 ◽  
Vol 03 (04) ◽  
pp. 1350033 ◽  
Author(s):  
Radheshyam Rai ◽  
Shweta Thakur ◽  
M. A. Valente ◽  
Andrei L. Kholkin
Keyword(s):  
Magnetic Properties ◽  
Solid State ◽  
Solid State Reaction ◽  
Magnetic Measurements ◽  
Ferroelectric Properties ◽  
Solid State Reaction Method ◽  
X Ray Diffraction ◽  
Solid State Reaction Technique ◽  
X Ray ◽  
Ceramic Samples

The multiferroic ( Bi 0.95 RE 0.05)( Fe 0.95 Mn 0.05) O 3 (where RE = Pr , Tb and Dy ) has been synthesized using solid-state reaction technique. Effects of Pr , Tb and Dy substitution on the structure, electrical and ferroelectric properties of ( Bi 0.95 RE 0.05)( Fe 0.95 Mn 0.05) O 3 samples have been studied by performing X-ray diffraction, dielectric measurements and magnetic measurements. The crystal structure of the ceramic samples have a monoclinic phase. The vibrating sample magnetometer (VSM) measurement shows a significant change in the magnetic properties of Pr -, Tb - and Dy -doped ( Bi 0.95 RE 0.05)( Fe 0.95 Mn 0.05) O 3. It is seen that coercive field (Hc) and remanent magnetization (Mr) increases for Pr but decreases for Dy and Tb .

Synthesis, characterization, and application of palladium complexes containing 8-quinolylphosphinite ligands

2010 ◽  
Vol 88 (2) ◽  
pp. 99-103 ◽  
Author(s):  
Earl Cook ◽  
Jason D. Masuda ◽  
Aibing Xia
Keyword(s):  
Solid State ◽  
Single Crystal ◽  
Phenylboronic Acid ◽  
Suzuki Coupling ◽  
Palladium Complexes ◽  
Aryl Halides ◽  
Coupling Reactions ◽  
X Ray Diffraction ◽  
X Ray ◽  
Solid State Structures

Palladium complexes containing 8-quinolylphosphinite ligands have been synthesized and characterized. Their solid state structures were determined by single-crystal X-ray diffraction. They were found to be active catalysts for Suzuki coupling reactions of phenylboronic acid and various aryl halides.

scholarly journals MicroED Elucidation of Diverse Solid-State Packing in a Family of Electron-Deficient Expanded Helicenes

2020 ◽  
Author(s):  
Adrian Samkian ◽  
Gavin R. Kiel ◽  
Christopher G. Jones ◽  
Harrison Bergman ◽  
Julia Oktawiec ◽  
...  
Keyword(s):  
Solid State ◽  
Electron Diffraction ◽  
Rapid Assessment ◽  
Nanometer Scale ◽  
Proof Of Concept ◽  
X Ray Diffraction ◽  
X Ray ◽  
Space Groups ◽  
Indispensable Tool ◽  
Solid State Structures

Solid-state packing plays a defining role in the properties of a molecular organic material, but it is difficult to elucidate in the absence of single crystals that are suitable for X-ray diffraction. Here, we demonstrate the coupling of divergent synthesis with microcrystal electron diffraction (MicroED) for rapid assessment of solid-state packing motifs, using a class of chiral nanocarbons – expanded helicenes – as a proof of concept. Two highly selective oxidative dearomatizations of a readily-accessible helicene provided a divergent route to four electron-deficient analogues containing quinone or quinoxaline units. Crystallization efforts consistently yielded microcrystals that were unsuitable for single crystal X-ray diffraction, but ideal for MicroED. This technique facilitated the elucidation of solid-state structures of all five compounds with <1.1 Å resolution. The otherwise-inaccessible data revealed a range of notable packing behavior, including four different space groups, homochirality in a crystal for a helicene with an extremely low enantiomerization barrier, and nanometer scale cavities. The results of this study suggest that MicroED will soon become an indispensable tool for high-throughput investigations in pursuit of next-generation organic materials.

scholarly journals Synthesis, Solid-state Structures, Solution Behaviour and Catalysis Studies of Nickel Complexes of Bis(benzimidazolin-2-ylidene)pyridine Pincer Ligands

2012 ◽  
Vol 65 (7) ◽  
pp. 823 ◽  
Author(s):  
Karen D. M. MaGee ◽  
Guy Travers ◽  
Brian W. Skelton ◽  
Massimilliano Massi ◽  
Alan D. Payne ◽  
...  
Keyword(s):  
Solid State ◽  
Single Crystal ◽  
Nickel Complexes ◽  
Pincer Ligands ◽  
X Ray Diffraction ◽  
Nmr Studies ◽  
X Ray ◽  
Solution Studies ◽  
Solid State Structures ◽  
Solution Behaviour

N-Heterocyclic carbene–nickel complexes with five- and four-coordinate geometries [(CNC)NiBr2] and [(CNC)NiBr]X (X = PF6 or BPh4) have been prepared with the pincer ligands 2,6-bis(N-octylbenzimidazolin-2-ylidene)pyridine and 2,6-bis(N-butyl-5,6-dimethoxybenzimidazolin-2-ylidene)pyridine. The addition of the n-octyl substituent significantly extends the solubility of the complexes and has allowed UV-vis solution studies of the complexes in dichloromethane and methanol. The four- and five-coordinate species exist in equilibrium in solution and this equilibrium has been explored by UV-vis studies. The complexes have also been characterized by NMR studies, and single crystal X-ray diffraction studies have been performed on [(CNC)NiBr2] (where CNC = 2,6-bis(N-octylbenzimidazolin-2-ylidene)pyridine) and [(CNC)NiBr]BPh4 (where CNC = 2,6-bis(N-butyl-5,6-dimethoxybenzimidazolin-2-ylidene)pyridine).

Magnetic and Structural Properties of Nanocomposite ZnO-Fe3O4 Films Prepared by Solid-State Synthesis

2014 ◽  
Vol 215 ◽  
pp. 158-162
Author(s):  
Liudmila E. Bykova ◽  
V.G. Myagkov ◽  
I.A. Tambasov ◽  
O.A. Bayukov ◽  
Victor S. Zhigalov ◽  
...  
Keyword(s):  
Electron Microscopy ◽  
Scanning Electron Microscopy ◽  
Solid State ◽  
Photoelectron Spectroscopy ◽  
Magnetic Measurements ◽  
X Ray Diffraction ◽  
Simple Method ◽  
Physical Methods ◽  
X Ray ◽  
Scanning Electron

A simple method for obtaining ZnO-Fe3O4 nanocomposites using solid-state reaction Zn + 3Fe2O3 ZnO + 2Fe3O4 is suggested. An analysis of the characteristics and properties of ZnO-Fe3O4 nanocomposites was carried out by a combination of structural and physical methods (X-ray diffraction, scanning electron microscopy, photoelectron spectroscopy, Mössbauer measurements, X-ray fluorescent analysis, and magnetic measurements). The magnetization of the hybrid ZnO-Fe3O4 films is equal to 440 emu/cm3. The resulting Fe3O4 nanoparticles are surrounded by a ZnO shell and have sizes ranging between 20 and 40 nm.

Synthesis of Ferromagnetic Germanides in 40Ge/60Mn Films: Magnetic and Structural Properties

2014 ◽  
Vol 215 ◽  
pp. 167-172
Author(s):  
Victor G. Myagkov ◽  
A.A. Matsunin ◽  
Y.L. Mikhlin ◽  
Victor S. Zhigalov ◽  
Liudmila E. Bykova ◽  
...  
Keyword(s):  
Solid State ◽  
Curie Temperature ◽  
Photoelectron Spectroscopy ◽  
Magnetic Measurements ◽  
Atomic Ratio ◽  
Photoelectron Spectra ◽  
Solid State Reactions ◽  
Ferromagnetic Phase ◽  
X Ray Diffraction ◽  
X Ray

Solid-state reactions between Ge and Mn films are systematically examined using X-ray diffraction, photoelectron spectroscopy and magnetic measurements. The films have a nominal atomic ratio Ge:Mn = 40:60 and are investigated at temperatures from 50 to 500 °С. It is established that after annealing at ~120 °С, the ferromagnetic Mn5Ge3 phase is the first phase to form at the 40Ge/60Mn interface. Increasing the annealing temperature to 500 °С leads to the formation of the ferromagnetic phase with a Curie temperature TC ~ 360 K and magnetization MS ~ 140-200 emu/cc at room temperature. Analysis of X-ray diffraction patterns and the photoelectron spectra suggests that the increased Curie temperature and magnetization are related to the migration of C and O atoms into the Mn5Ge3 lattice and the formation of the Nowotny phase Mn5Ge3СxOy. The initiation temperature (~120 °С) of the Mn5Ge3 phase is the same both for solid-state reactions in Ge/Mn films, as well as for phase separation in GexMn1-x diluted semiconductors. We conclude that the synthesis of the Mn5Ge3 phase is the moving force for the spinodal decomposition of the GexMn1-x diluted semiconductors.

Sign in / Sign up

Export Citation Format

Share Document