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51.
New ONS hydrazone ligand, 2-[(2-aminochromon-3-yl)methylidene]-N-phenylhydrazinecarbothioamide, HL , was synthesized and reacted with different salts of Cu (II) ion (OAc−, NO3−, SO42− and Cl−) in absence and presence of secondary ligands (L′); 8-hydroxyquinoline, 1,10-phenanthroline or SCN−; to form binary and ternary Cu(II)-chelates. The ligand and its Cu(II)-complexes were fully characterized by analytical, spectral, thermal, conductivity and magnetic susceptibility measurements. The metal chelates showed octahedral, square planar and /or distorted tetraherdal arrangements. Coats–Redfern equations used to calculate the kinetic parameters of the thermal decomposition stages (Ea, A, ΔH, ΔS and ΔG). The compounds exhibit luminescence property; promising interesting potential applications as photoactive materials. Lippert–Mataga, Bakhshiev, Kawski–Chamma–Viallet and microscopic solvent polarity parameter and ETN correlation methods were applied on the solvatochromic shifts of emission spectra to evaluate the ground (μg) and excited (μe) states dipole moments. Excited state dipole moment is larger than the ground state which may be attributed to π-π* transition. The coordinating anions play an important role on the position and intensity of emission band. The ligand and its metal complexes showed antimicrobial activity towards Gram–positive bacteria, Gram–negative bacteria, yeast and fungus. The molecular structural parameters of HL and its Cu(II)- complexes have been calculated on the basis of DFT engaged in the Gaussian 09 program at the B3LYP/6-31G(d,p) level; the theoretical data are correlated with the experimental data. 相似文献
52.
A robust 4,8-connected Tb-based metal-organic framework (Tb-MOF) with paddle wheel-shaped {Tb2(COO)4} subunits extended by C3-symmetric 3,3',3''-[1,3,5-benzenetriyltris(carbonylimino)]tris-benzoate connector was hydrothermally synthesized, showing highly environmental stability, good dispersion and intense green emission in water system. Resulting critically from the well suppressed absorption towards the excitation energy, the Tb-MOF exhibits rapid and efficient fluorescent response towards nitroimidazole antibiotics with strong quenching constants and low detection limits of 1.59 × 104 m –1 and 2.4 μM for metronidazole as well as 1.62 × 104 m –1 and 2.9 μM for dimetridazole. Moreover, the sensitive and selective identification of the Tb-MOF has strong anti-interference and excellent regeneration ability, which endows the promising applications of the Tb-MOF as fluorescent sensing materials. 相似文献
53.
Considering the importance of silylene ligands in transition metal-mediated catalytic reactions, we have scrutinized eight novel monodentate ( 1 – 4 ) and bidentate ( 1 ′ - 4 ′ ) derivatives of 2,5-diX-cyclopentasilylene-2,4-dienes (X = NH2, OH, PH2, and SH), at M06/6-311++G** level of theory. To probe the complexation ability of our scrutinized silylene ligands with Rh atom ( 1 Rh - 4 Rh and 1 ′ Rh - 4 ′ Rh , respectively), thermodynamic and structural parameters such as complexation energy (ΔECom), singlet-triplet energy gap (ΔEs-t), bond length, along with NBO and atoms in molecules analyses are provided. In going from less electron donating groups (EDGs) to more EDGs (NH2 > OH > PH2 > SH), the σ -donor strength and ligand flexibility increase. Structures 1 and 1 ′ turn out as the most nucleophilic species for showing the highest nucleophilicity (N = 5.47 and 5.40 eV, respectively). Furthermore, they exhibit the highest proton affinity values (PA = 271.46 and 271.23 kcal/mol, respectively). The results indicate that bidentate coordination mode of silylene leads to a stronger Si-Rh complex. The overall orders of σ -donation ability for monodentate and bidentate silylene ligands are 1 > 2 > 3 > 4 and 1 ′ > 2 ′ > 3 ′ > 4 ′ , respectively. 相似文献
54.
Fabio Cameli Prof. Dr. Joop H. ter Horst Dr. René R. E. Steendam Dr. Ir. Christos Xiouras Prof. Dr. Georgios D. Stefanidis 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(6):1344-1354
Herein, the pivotal role of secondary nucleation in a crystallization-enhanced deracemization process is reported. During this process, complete and rapid deracemization of chiral conglomerate crystals of an isoindolinone is attained through fast microwave-assisted temperature cycling. A parametric study of the main factors that affect the occurrence of secondary nucleation in this process, namely agitation rate, suspension density, and solute supersaturation, confirms that an enhanced stereoselective secondary nucleation rate maximizes the deracemization rate. Analysis of the system during a single temperature cycle showed that, although stereoselective particle production during the crystallization stage leads to enantiomeric enrichment, undesired kinetic dissolution of smaller particles of the preferred enantiomer occurs during the dissolution step. Therefore, secondary nucleation is crucial for the enhancement of deracemization through temperature cycles and as such should be considered in further design and optimization of this process, as well as in other temperature cycling processes commonly applied in particle engineering. 相似文献
55.
Cyrille Charpentier Jérémy Salaam Dr. Aline Nonat Fabio Carniato Dr. Olivier Jeannin Dr. Isabel Brandariz Dr. David Esteban-Gomez Dr. Carlos Platas-Iglesias Dr. Loïc J. Charbonnière Prof. Mauro Botta 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(24):5407-5418
The heptadentate ligand L was shown to form an extremely stable Gd complex at neutral pH with a pGd value of 18.4 at pH 7.4. The X-ray crystal structures of the complexes formed with Gd and Tb displayed two very different coordination behaviors being, respectively, octa- and nonacoordinated. The relaxometric properties of the Gd complex were studied by field-dependent relaxivity measurements at various temperatures and by 17O NMR spectroscopy. The pH-dependence of the longitudinal relaxivity profile indicated large changes around neutral pH leading to a very large value of 10.1 mm −1⋅s−1 (60 MHz, 298 K) at pH 4.7. The changes were attributed to an increase of the hydration number from one water molecule in basic conditions to two at acidic pH. A similar trend was observed for the luminescence of the Eu complex, confirming the change in hydration state. DOSY experiments were performed on the Lu analogue, pointing to the absence of dimers in solution in the considered pH range. A breathing mode of the complex was postulated, which was further supported by 1H and 31P NMR spectroscopy of the Yb complex at varying pH and was finally modeled by DFT calculations. 相似文献
56.
Hyunchang Park Prof. Dr. Dongwhan Lee 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(27):5916-5926
Novel functions emerge from novel structures. To develop efficient catalytic systems for challenging chemical transformations, chemists often seek inspirations from enzymatic catalysis. A large number of iron complexes supported by nitrogen-rich multidentate ligands have thus been developed to mimic oxo-transfer reactivity of dioxygen-activating metalloenzymes. Such efforts have significantly advanced our understanding of the reaction mechanisms by trapping key intermediates and elucidating their geometric and electronic properties. Critical to the success of this biomimetic approach is the design and synthesis of elaborate ligand systems to balance the thermodynamic stability, structural adaptability, and chemical reactivity. In this Concept article, representative design strategies for biomimetic atom-transfer chemistry are discussed from the perspectives of “ligand builders”. Emphasis is placed on how the primary coordination sphere is constructed, and how it can be elaborated further by rational design for desired functions. 相似文献
57.
Pedro D. García-Fernández Cristina Izquierdo Dr. Javier Iglesias-Sigüenza Dr. Elena Díez Prof. Rosario Fernández Prof. José M. Lassaletta 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(3):629-633
The formal insertion of alkenes into aromatic chloro- and bromoalkynes takes place under cationic gold catalysis. This haloalkynylation reaction can be performed with cyclic, gem-disubstituted and monosubstituted alkenes, using BINAP, triazolo[4,3-b]isoquinolin-3-ylidene ligands or SPhos, respectively. The products were isolated in moderate to excellent yields and with complete diastereo- and regioselectivity; the halogen atom bonding the more substituted carbon of the alkene. Preliminary experiments showed that the enantioselective haloalkynylation of cyclopentene can be performed with (S)-BINAP to afford the insertion products with moderate to good enantioselectivities. 相似文献
58.
Jin Tanaka Yu Shibata Anton Joseph Juntaro Nogami Jyunichi Terasawa Ryo Yoshimura Prof. Dr. Ken Tanaka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(26):5774-5779
It has been established that a newly developed cyclopentadienyl rhodium(III) [CpARhIII] complex, bearing an acidic secondary amide moiety on the Cp ring, is able to catalyze the ortho-bromination of O-phenyl carbamates with N-bromosuccinimide (NBS) at room temperature. The presence of the acidic secondary amide moiety on the CpA ligand accelerates the bromination by the hydrogen bond between the acidic NH group of the CpA ligand and the carbonyl group of NBS. 相似文献
59.
Raoul Plessius Vera Deij Prof. Dr. Joost N. H. Reek Prof. Dr. Ir. Jarl Ivar van der Vlugt 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(58):13241-13248
Three Pt4L2L′2 heteroleptic rectangles ( 1 – 3 ), containing ditopic redox-active bis-pyridine functionalized perylene bisimide (PBI) ligands PBI-pyr2 ( L ) are reported. Co-ligand L′ is a dicarboxylate spacer of varying length, leading to modified overall size of the assemblies. 1H NMR spectroscopy reveals a trend in the splitting and upfield chemical shift of the PBI-hydrogens in the rectangles with respect to free PBI, most pronounced with the largest strut length ( 3 ) and least with the smallest strut length ( 1 ). This is attributed to increased rotational freedom of the PBI-pyr 2 ligand over its longitudinal axis (Npy-Npy), due to increased distance between the PBI-surfaces, which is corroborated by VT-NMR measurements and DFT calculations. The intramolecular motion entails desymmetrization of the two PBI-ligands, in line with cyclic voltammetry (CV) data. The first (overall two-electron) reduction event and re-oxidation for 1 display a subtle peak-to-peak splitting of 60 mV, whilst increased splitting of this event is observed for 2 and 3 . The binding of pyrene in 1 is probed to establish proof of concept of host-guest chemistry enabled by the two PBI-motifs. Fitting the binding curve obtained by 1H NMR titration with a 1:1 complex formation model led to a binding constant of 964±55 m −1. Pyrene binding is shown to directly influence the redox-chemistry of 1 , resulting in a cathodic and anodic shift of approximately 46 mV on the first and second reduction event, respectively. 相似文献
60.
Dr. Subrat Kumar Barik Shou-Chih Huo Chun-Yen Wu Tzu-Hao Chiu Jian-Hong Liao Dr. Xiaoping Wang Dr. Samia Kahlal Prof. Jean-Yves Saillard Prof. C. W. Liu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(46):10471-10479
Although atomically precise polyhydrido copper nanoclusters are of prime interest for a variety of applications, they have so far remained scarce. Herein, this work describes the synthesis of a dithiophosphate-protected copper(I) hydride-rich nanocluster (NC), [Cu30H18{S2P(OnPr)2}12] ( 1H ), fully characterized by various spectroscopic methods and single-crystal X-ray diffraction. The X-ray structure of 1H reveals an unprecedented central Cu12 hollow icosahedron. Six faces of this icosahedron are capped by Cu3 triangles, the whole Cu30 core being wrapped by twelve dithiophosphate ligands and the whole cluster has ideal S6 symmetry. The locations of the 18 hydrides in 1H were ascertained by a single-crystal neutron diffraction study. They are composed of three types: capping μ3-H, interstitial μ4-H (seesaw) and μ5-H ligands (square pyramidal), in good agreement with the DFT simulations. The numbers of hydrides and ligand resonances in the 1H NMR spectrum of 1H are in line with their coordination environment in the solid state, retaining the S6 symmetry in solution. Furthermore, two new Se-protected polyhydrido copper nanoclusters, [Cu30H18{Se2P(OR)2}12] ( 2H : R=iPr 3H : R=iBu) were synthesized from their sulfur relative 1H via ligand displacement reaction and their X-ray structures feature the exceptional case where both the NC shape and size are fully conserved during the course of ligand exchange. DFT and TD-DFT calculations allow understanding the bonding and optical properties of clusters 1H – 3H . In addition, the reaction of 1H with [Pd(PPh3)2Cl2] in the presence of terminal alkynes led to the formation of new bimetallic Cu−Pd alloy clusters [PdCu14H2{S2P(OnPr)2}6(C≡CR)6] ( 4 : R=Ph; 5 : R = C6H4F). 相似文献