Substituent effect in unsymmetrical lutetium bisphthalocyanines: a DFT analysis

International audienceDFT calculations have been carried out on a series of unsymmetrical bisphthalocyanine lutetium complexes in which one of the ligands is substituted by 8 or 16 chlorine atoms. It is shown that their unpaired electron is predominantly localized on the non-substituted ligand. An orbital explanation is provided to rationalize this effect. A good agreement is found between the computed and experimental ionization potentials and electroaffinities and the redox potentials of a closely related series, as well as between their TDDFT-computed and experimental UV-visible transitions which are analysed

Reaction Mechanisms of Transition-Metal-Catalyzed Azide-Alkyne Cycloaddition “Click” Reactions: A DFT Investigation

International audienceDFT calculations at the PBE0/LANL2DZ level have been performed on model compounds to investigate the reaction mechanism of two recently reported metal-catalyzed alkyne azide cycloaddition (MAAC). The first one, that involves a [Cu(tren)]+Br- catalyst, is shown not to proceed through a metal alkynyl intermediate, but, after precomplexation of the alkyne in an η2-mode, directly to the 1,4-disubstituted 1,2,3-triazole product, through a metallacyclic transition state. The other system, involving a rare-earth Ln[N(SiMe3)2]3 complex, is found to proceed through an alkynyl-azide complex which produces an η 2-coordinated heterocyclic ligand before protonation by an incoming alkyne molecule. Our results are discussed with respect to other computational data from the literatur

An eleven-vertex deltahedron with hexacapped trigonal bipyramidal geometry.

International audienceThe first elemental cluster with hexacapped trigonal bipyramidal geometry is revealed in the luminescent undecanuclear silver complex which is stabilized by nine dithiocarbamate ligands and has an interstitial hydride. The hydride position within the Ag(11) cage is confirmed by a DFT investigation

Electronic structure and metal-metal communication in (CpM)2(as-indacene) and (CpM)2(s-indacene) (M = Mn, Fe, Co, Ni) complexes: a DFT investigation

International audienceDFT calculations with full geometry optimization have been performed on the series (CpM)2(as-indacene) and (CpM)2(s-indacene) (M = Mn, Fe, Co, Ni), as well as on the cations of the Fe, Co and Ni complexes. The compounds where M = Fe and Ni (as-indacene series) and M = Mn, Fe and Co (s-indacene series) were found to possess closed-shell ground states. In the mixed-valent cations as well as in the other open-shell species, the degree of metal-metal communication and the participation of the ligand into the spin density were evaluated. In general, the larger the total electron number, the larger the metal-metal communication and ligand participation to the frontier orbitals

DFT study of dihydrogen addition to molybdenum π-heteroaromatic complexes: a prerequisite step for the catalytic hydrodenitrogenation process

International audienceThe range of molybdenum hydride complexes that are sought to participate in the important catalytic hydrodenitrogenation process (HDN) of nitrogen containing polycyclic aromatic hydrocarbons were evaluated by DFT studies. The previously synthesized stable (η6-quinoline)Mo(PMe3)3 complex 1N, in which molybdenum is bonded to the heterocyclic ring, was chosen as a model. The hydrogenation of the quinone heterocycle, which was postulated as the initial step in the overall HDN reaction, is found to occur via three consecutive steps of the oxidative addition of dihydrogen to Mo in 1N. Successive transfer of hydrogen atoms from the metal to the heterocycle leads to the ultimate formation of the tetrahydrido molybdenum intermediate Mo(PMe3)4H413 and 2,2,3,3-tetrahydroquinoline C9H11N 14. All the involved intermediates and transition states have been fully characterized by DFT. This computational modeling of the hydrogenation of quinoline, as a part of extended HDN catalytic processes, provides a fundamental understanding of such mechanism

Copper Clusters Containing Hydrides in Trigonal Pyramidal Geometry

International audienceStructurally precise copper hydrides [CuH{SP(OPr)}(C≡CR)], R = Ph (1), CHF (2), and CHOMe (3), were first synthesized from the polyhydrido copper cluster [CuH{SP(OPr)}] with nine equivalents of terminal alkynes. Later, their isolated yields were significantly improved by direct synthesis from [Cu(CHCN)](PF), [NH][SP(OPr)], NaBH, and alkynes along with NEt in THF. 1, 2, and 3 were fully characterized by single-crystal X-ray diffraction, ESI-MS, and multinuclear NMR spectroscopy. All three clustershave 11 copper atoms, adopting 3,3,4,4,4-pentacapped trigonal prismatic geometry, with two hydrides inside the Cu cage, the position of which was ascertained by a single-crystal neutron diffraction structure of cluster 1 co-crystallized with a [Cu(H){SP(OPr)}] (4) cluster. Six dithiophosphate and three alkynyl ligands stabilize the CuH core in which the two hydrides adopt a trigonal pyramidal coordination mode. This coordination mode is so far unprecedented for hydride. The H NMR resonance frequency of the two hydrides appears at 4.8 ppm, a value further confirmed by H NMR spectroscopy for their deuteride derivatives [Cu(D){SP(OPr)}(C≡CR)]. A DFT investigation allows understanding the bonding within this new type of copper(I) hydrides

Synthesis, characterization and third-order nonlinear optical properties of a dodecaruthenium organometallic dendrimer with a zinc(ii) tetraphenylporphyrin core

A new Zn(ii) porphyrin-based dendrimer (5(2)) containing twelve Ru(ii) alkynyl fragments, has been prepared following a convergent approach in two steps from 5,10,15,20-tetra(4-ethynylphenyl)porphyrinatozinc(ii) (6). The cubic nonlinear optical (NLO) properties of 5(2) and other derivatives of 6 have been measured by third-harmonic generation (THG) at 1907 nm and by Z-scan over the spectral range 500-1700 nm, revealing the remarkable NLO response of 5(2) in the near-IR range. These results highlight the beneficial role of the extended cross fourchee-like polymetallic structure of 5(2) on its third-order NLO properties.This research was supported by grants from the “Region Bretagne” (A. M. and G. G.) and the Australian Research Council (M. G. H.). The CNRS (PICS programs No. 5676 & 7106 and LIA Redochrom) and UEB/FEDER/RTR-Bresmat (EOPT 11MF422-02 Porphamp) are acknowledged for financial support. T. G., S. K. and J.-F. H. thank GENCI (Grand Equipment National de Calcul Intensif ) for HPC resources project GENCI A0030807367-gen7367). Drs. M. Reynolds (UMR 8537), A. Bondon and O. Mongin (UMR 6226) are acknowledged for assistance during spectroscopic characterizations

Zwitterionic Mixed-Valence Species for the Design of Neutral Clocked Molecular Quantum-Dot Cellular Automata

International audienceMixed-valence compounds can be used for the design of molecular quantum-dot cellular automata (QCA). Here, we investigate the QCA properties of a three-dot "Y"-shaped functionalized zwitterionic neutral -carborane model 1-(3,5-{Cp(dHpe)Fe-C≡C-}(CH))-10-Cp(dHpe)Fe-C≡C--1-CBH () (Cp = cyclopentadienyl (η-CH) and dHpe = 1,2-bis(phosphino)ethane (HPCHCHPH)) as a neutral clocked molecular half-cell. DFT results clearly demonstrate that can display simultaneously the two most basic properties necessary for clocked QCA operation, i.e., bistable switching behavior and clocked control. This is possible due to the three stable states (two active and one null) of , corresponding to occupation of each of the three iron-ethynyl groups by the positive charge. In addition, the proximal electronic bias effects can be overcome by the zwitterionic nature of , which could be imposed by external counterions, rendering these effects more predictable