7 research outputs found
Iridium(I)/N-Heterocyclic Carbene Hybrid Materials: Surface Stabilization of Low-Valent Iridium Species for High Catalytic Hydrogenation Performance
An Ir-I(NHC)-based hybrid material was prepared using a methodology which allowed the precise positioning and isolation of the Ir centers along the pore channels of a silica framework. The full characterization of the material by solid-state NMR spectroscopy showed that the supported Ir sites were stabilized by the silica surface, as low-coordinated single-site complexes. The material is extremely efficient for the hydrogenation of functional alkenes. The catalytic performance (TOF and TON) is one to two orders of magnitude higher than those of their molecular Ir analogues, and could be related to the prevention of the bimolecular deactivation of Ir complexes observed under homogeneous conditions
The case of a Cd2Cu2 complex containing an apparently C3-symmetric ligand : Erroneous ligand-structure assignment by X-ray diffraction data analysis
International audienc
Phosphine-based push-pull AIE fluorophores: Synthesis, photophysical properties, and TD-DFT studies
International audienceAbstract When periodically packing the intramolecular donor-acceptor structures to form ferroelectric-like lattice identified by second harmonic generation, our CD49 molecular crystal shows long-wavelength persistent photoluminescence peaked at 542ânm with the lifetime of 0.43âs, in addition to the short-wavelength prompt photoluminescence peaked at 363ânm with the lifetime of 0.45âns. Interestingly, the long-wavelength persistent photoluminescence demonstrates magnetic field effects, showing as crystalline intermolecular charge-transfer excitons with singlet spin characteristics formed within ferroelectric-like lattice based on internal minority/majority carrier-balancing mechanism activated by isomer doping effects towards increasing electron-hole pairing probability. Our photoinduced Raman spectroscopy reveals the unusual slow relaxation of photoexcited lattice vibrations, indicating slow phonon effects occurring in ferroelectric-like lattice. Here, we show that crystalline intermolecular charge-transfer excitons are interacted with ferroelectric-like lattice, leading to exciton-lattice coupling within periodically packed intramolecular donor-acceptor structures to evolve ultralong-lived crystalline light-emitting states through slow phonon effects in ferroelectric light-emitting organic crystal
Unexpected Structure of a Helical N 4 -Schiff-Base Zn(II) Complex and Its Demetallation: Experimental and Theoretical Studies
International audienceA new ZnâN4âSchiff base L=((±)âtransâN,NââBis(2âaminobenzylidene)â1,2âdiaminocyclohexane) complex was synthesized and fully characterized, showing an unexpected selfâassembled doubleâstranded helicate structure. The Xâray crystal analysis of the Zn2L2 complex ((C40H44N8Zn2,CH2Cl2, a=14.2375(3) Ă
, b=16.7976(4) Ă
, c=16.1613(4) Ă
, monoclinic, P21/n, Z=4) shows a centrosymmetrical structure in which zinc atoms are in distorted tetrahedral environments, revealing an Mâ (R, R) leftâhanded helicity in its asymmetric unit. However, it was observed that this dinuclear complex is thermodynamically unstable in the presence of small water amounts and undergoes demetallation into free N4âSchiff base ligand and ZnO nanoparticles. This hydrolysis process was thoroughly identified and monitored through detailed 1H NMR, DOSY NMR analysis. The reaction mechanism of this demetallation event was elucidated by using the DFT method, involving an activation energy smaller than 13â
kcal/mol. Besides, a theoretical mechanism of the demetallation process is given for the first time
Sensitive 1,1-dicyanovinyl push-pull dye for primary amine sensing in solution by fluorescence
International audienc
Titanacalixarenes in Homogeneous Catalysis: Synthesis, Conformation and Catalytic Activity in Ethylene Polymerisation
International audienceVariously substituted titanacalixarenes were synthesised and tested for their performance as catalysts in ethylene polymerisation: p-tert-butylcalix[4]arene was derivatised to afford distal diether p-tert-butylcalix[4]arenes L1âL4, distal dihydroxy-depleted L5, proximal dihydroxy-depleted L6, proximal diether p-tert-butylcalix[4]arene L7, proximal intrabridged disiloxane L8 and proximal monoether L9. (Dichlorotitana)-p-tert-butylcalix[4]arenes 1â8 and (monochlorotitana)-p-tertbutylcalix[4]arene 9 have been successfully synthesised by reacting L1âL4 with TiCl4·2THF or L5âL9 with TiCl4. The structural conformation of complexes 1â9 in solution were determined by 1H NMR, 13C NMR, NOESY and COSY spectroscopic studies. Compounds 2, 3 and 4 have been structurally characterised by single-crystal X-ray diffraction. Upon activation with methylaluminoxane, compounds 1â8 revealed low to moderate activities for the production of high-density polyethylene (HDPE) to ultra-high-molecular-weight polyethylene (UHMWPE). 6/MAO gave the best activity at 770 kgPEâ(molâTi)â1âhâ1
Synthesis of novel tantalacalixarene complexes: first example of intramolecular CH activation of monodepleted aromatic ring
International audienceThe alkylation of (dichlorotantala)-p-tert-butylcalix[4]arenes 1 and 3 by two equivalents of NpMgCl (Np = neopentyl) affords the corresponding unreported (bisneopentyltantala)-p-tert-butylcalix[4]arenes 4 and S. These complexes can undergo dealkylation by modest increase of the temperature to yield 6 and 7. The characterization and structural conformation of the complexes 6 and 7 were determined by H-1, C-13, NOESY, and COSY spectroscopic studies and single-crystal X-ray diffraction. 7 exhibits unprecedented use of an intramolecular C H activation of an aromatic ring and simultaneously releases of one equivalent of neopentane. DFT calculation supports a mechanism in which the metal passes through a transition state involving a coplanar arrangement with its three ligands (C-Ar, H-Ar., C-Np)