Search results for "SPECT"

NMR T1-Relaxation Measurements on Paramagnetic Organolanthanides: An Alternative Tool for Structure Determination in Solution

2005

1H NMR investigations were conducted on four paramagnetic organolanthanides, all bearing the tetraisopropylcyclopentadienyl ligand Cp4i (HC5iPr4) in order to verify whether or not interactions observed in the solid state are maintained in solution. In some cases variable-temperature experiments were necessary to enhance the resolution and determine the best conditions for the study. The 1D NMR spectrum could be interpreted in every case. Complementary 2D COSY experiments allowed the full attribution of the signals. T1 (1H) relaxation values were determined for all the paramagnetic complexes at the most suitable temperature, and compared with those of the diamagnetic KCp4i. The same tendency…

2021

A nickel complex incorporating an N2 O ligand with a rare η2 -N,N'-coordination mode was isolated and characterized by X-ray crystallography, as well as by IR and solid-state NMR spectroscopy augmented by 15 N-labeling experiments. The isoelectronic nickel CO2 complex reported for comparison features a very similar solid-state structure. Computational studies revealed that η2 -N2 O binds to nickel slightly stronger than η2 -CO2 in this case, and comparably to or slightly stronger than η2 -CO2 to transition metals in general. Comparable transition-state energies for the formation of isomeric η2 -N,N'- and η2 -N,O-complexes, and a negligible activation barrier for the decomposition of the lat…

Three‐in‐One Crystal: The Coordination Diversity of Zinc Polypyridine Complexes

2017

The synthesis, structural and photophysical properties of two novel zinc(II) complexes bearing the tridentate ddpd (N,N' dimethyl N,N' dipyridin 2 ylpyridine 2,6 diamine) ligand are presented. Structural investigations have been carried out by single crystal X-ray diffractometry, NMR spectroscopy and Density Functional Theory calculations, revealing a diverse coordination behavior depending on the counter ion. Spectroscopic (UV-VIS and emission spectroscopy) and theoretical techniques (density functional theory and time dependent DFT calculations) have been employed to explore the photophysical properties of the complexes.

Structure effects induced by high mechanical compaction of STAM-17-OEt MOF powders

2021

Financial support by PJ-RIC-FFABR_2017 and the EPSRC grant EPSRC industrial CASE award (grant EP/N50936X/1) are acknowledged. The research programme Nanoporous materials (P1-0021) financially supported by Slovenian Research Agency (ARRS) is acknowledged as well. Metal-organic frameworks (MOFs) are promising materials for many potential applications, spacing from gas storage to catalysis. However, the powder form of which they are generally made is not suitable, mainly because of the low packing density. Powder compaction is therefore necessary, but also challenging because of their typical mechanical fragility. Indeed, generally, they undergo irreversibly damages upon densification processe…

X-ray, conformation and electronic structures of 1-nitropyrrolidine

2016

Abstract The chemistry of pyrrolidine compounds has drawn much attention because of their biological activities. The crystal and molecular structure of 1-nitropyrrolidine (C4H8NNO2) at 150K, along with calculated structures (DFT and MP2), are reported herein. In the solid-state, the asymmetric part of the unit cell is composed of one quartermolecule at the position of two perpendicular mirror planes and the five-membered ring is disordered over a mirror plane, revealing the twisted conformation. Both geometries suggest slight sp3 hybridization of the amine nitrogen atom. The non-planar geometry suggests the lack of conjugation of the amine nitrogen lone pair with the nitro group, however th…

Regioselective Synthesis of Mono- and Dispiropyrazoline Derivatives via 1,3-dipolar Cycloaddition with Nitrilimines

2016

The 1,3-dipolar cycloaddition reaction of (E,E)-1,3-bis(arylidene)indan-2-one with diarylnitrilimines, generated in situ via dehydrohalogenation of the corresponding hydrazonoyl chlorides , affords predominantly monospiropyrazolines and as a mixture of diastereoisomers. Also dispiropyrazolines are formed in moderate yields. The structure and stereochemistry of cycloadducts were confirmed by 1H and 13C-NMR spectroscopy, elemental analyses data, and single-crystal X-ray diffraction studies of and .

Photocatalytic Giese Addition of 1,4-Dihydroquinoxalin-2-ones to Electron-Poor Alkenes Using Visible Light.

2020

The visible-light photoredox-catalyzed coupling of 1,4-dihydroquinoxalin-2-ones and Michael acceptors was achieved using Ru(bpy)3Cl2 as the photocatalyst and (PhO)2PO2H as an additive. The optimized reaction conditions provide a good yield for the radical conjugate addition products (44 examples) with a wide range of structurally different Michael acceptors. A gram scale reaction using sunlight irradiation is also described. Furthermore, several transformations were carried out with the Giese addition products.

Effect of quaternary ammonium salts on spectral properties of zinc octacarboxyphthalocyanine

2020

Abstract The paper presents results of the research on the influence of quaternary ammonium salts on UV–vis absorption and emission spectra of zinc octacarboxyphthalocyanine (ZnPcOC). Quaternary ammonium salts which show biological activity play a crucial role. In ZnPcOC solutions with a proper concentration of tetrabutylammonium salts (TBAX), a strong bathochromic shift band (λmax = 760 nm – “R” band) showing red fluorescence appears in time. The presence of tetrabutylammonium salt causes pH increase and, consequently, a gradual dissociation of carboxyl groups in ZnPcOC molecule. It seems that –COO— anions present in the ZnPcOC complex can interact with tetraalkylammonium cations, causing …

Thermo-Chromium: A Contactless Optical Molecular Thermometer.

2017

The unparalleled excited-state potential-energy landscape of the chromium(III)-based dye [1]3+ ([Cr(ddpd)2 ]3+ ; ddpd=N,N'-dimethyl-N,N'-dipyridin-2-yl-pyridin-2,6-diamine) enables a strong dual emission in the near infrared region. The temperature dependence of this dual emission allows the use of [1]3+ as an unprecedented molecular ratiometric thermometer in the 210-373 K temperature range in organic and in aqueous media. Incorporation of [1]3+ in biocompatible nanocarriers, such as 100 nm-sized polystyrene nanoparticles and solutol micelles, provides nanodimensional thermometers operating under physiological conditions.

Organotin(IV) derivatives containing heteroditopic pyridyl-quinolin-8-olate ligands: Synthesis and structures

2021

Abstract Six novel neutral organotin(IV) complexes, viz. [n-Bu2Sn(L4-PyAQ)2] 1, [Bz2Sn(L4-PyAQ)2] 2, [Ph2Sn(L4-PyAQ)2] 3, [Ph2Sn(L3-PyAQ)2] 4, [Bz3Sn(L4-PyAQ)] 5 and [Ph3Sn(L4-PyAQ)] 6 have been synthesized via reactions of 3/4-pyridyl-quinolin-8-ol pro-ligands, with appropriate diorganotin oxide and triorganotin hydroxide precursors, respectively. The compounds 1-6 were characterized in solution by means of NMR spectroscopy while the solid-state structures of 1, 6, and of the solvates 2·1.5C6H6, 3·0.25C6H6, 2·4·C6H6, and 5·0.5H2O were authenticated by single crystal X-ray diffraction analysis. In the solid-state, the tin centers in 1-2·4·C6H6 are hexacoordinated and reveal a distorted cis-…