A rare three-coordinated zinc cluster-organic framework with two types of secondary building units.

A rare chiral 3D cluster-organic framework {[Zn17O5(NTB)6(NDB)3]·41H2O}n () (H3NTB = 4,4',4''-nitrilotrisbenzoic acid and H2NDB = 4,4'-nitrilodibenzoic acid) was prepared and structurally characterized. Complex contains two types of [Zn4(µ4-O)(COO)6] and unreported [Zn9(µ3-O)3(COO)12] SBUs, which link bi- and tri-carboxylic acids and extend to an unprecedented (3,6,12)-connected framework. In addition, electronic structure calculations were performed to scrutinize the features of embedded clusters.

A remarkable cis- and trans-spanning dibenzylidene acetone diphosphine chelating ligand (dbaphos).

A multidentate and flexible diolefin-diphosphine ligand, based on the dibenzylidene acetone core, namely dbaphos (1), is reported herein. The ligand adopts an array of different geometries at Pt, Pd and Rh. At Pt(II) the dbaphos ligand forms cis- and trans-diphosphine complexes and can be defined as a wide-angle spanning ligand. (1)H NMR spectroscopic analysis shows that the ß-hydrogen of one olefin moiety interacts with the Pt(II) centre (an anagostic interaction), which is supported by DFT calculations. At Pd(0) and Rh(I), the dbaphos ligand exhibits both olefin and phosphine interactions with the metal centres. The Pd(0) complex of dbaphos is dinuclear, with bridging diphosphines. The complex exhibits the coordination of one olefin moiety, which is in dynamic exchange (intramolecular) with the other "free" olefin. The Pd(0) complex of dbaphos reacts with iodobenzene to afford trans-[Pd(II)(dbaphos)I(Ph)]. In the case of Rh(I), dbaphos coordinates to form a structure in which the phosphine and olefin moieties occupy both axial and equatorial sites, which stands in contrast to a related bidentate olefin, phosphine ligand ("Lei" ligand), in which the olefins occupy the equatorial sites and phosphines the axial sites, exclusively.

A theoretical study of the mechanism for the homogeneous catalytic reversible dehydrogenation-hydrogenation of nitrogen heterocycles.

A mechanism for the dehydrogenation reaction of 1,2,3,4-tetrahydroquinoline to quinoline derivatives, catalyzed by a Cp*Ir complex containing a 2-pyridonate ligand, is proposed and supported by theoretical calculations at the B3LYP level. The proposed mechanism involves two stages which are all thermodynamically unfavorable (endothermic by 36.3 kcal mol(-1) and 18.4 kcal mol(-1), respectively). The apparent activation energies of the first and second stages of the reaction are 30.8 kcal mol(-1) and 34.0 kcal mol(-1), respectively, and are considered overestimates of the entropy change of reaction. Owing to a decrease in the oxidative ability of iridium(III) coordinated to large electronegative nitrogen and chlorine, ligand promoted hydrogen abstraction is crucial at both stages of dehydrogenation, in which the oxidation state of iridium(III) does not change, and the ligand 2-pyridonate is converted to 2-hydroxypyridine. Cp*Ir(C(5)NH(4)OH)ClH, an important intermediate, releases hydrogen through an energy barrier of 23.5 kcal mol(-1).

Theoretical study of one- and two-photon absorption properties of octupolar D2d and D3 bipyridyl metal complexes.

The molecular equilibrium structures, electronic structures, and one- and two-photon absorption (TPA) properties of C2v (Zn(II), Fe(II) and Cu(I)) dipolar and D2d (Zn(II) and Cu(I)) and D3 (Zn(II)) octupolar metal complexes featuring different functionalized bipyridyl ligands have been studied by the ZINDO-SOS method. The calculated results show that one- and two-photon absorption properties of metal complexes are strongly influenced by the nature of the ligands (donor end groups and pi linkers) and metal ions as well as by the symmetry of the complexes. The length of the pi-conjugated backbone, the Lewis acidity of the metal ions, and the increase of ligand-to-metal ratio result in a substantial enhancement of the TPA cross sections of metal complexes. Substitution of C=N and N=N for C=C plays an important role in altering the maximum TPA wavelengths and the maximum TPA cross sections of metal complexes. Of them, the C=N substituted metal complexes have relatively large TPA cross sections. Replacing styryl with thienylvinyl makes the one-photon absorption wavelength red shift and at the same time leads to a great decrease of the maximum TPA cross sections of metal complexes. The possible reason is discussed. In the range 500-1250 nm, octupolar metal complexes exhibit intense TPAs and therefore are promising candidates for TPA materials.

Theoretical study of two-photon absorption properties of a series of ferrocene-based chromophores.

The electronic structures, one-photon absorption (OPA), and two-photon absorption (TPA) properties of a series of ferrocene-based chromophores with TCF-type acceptors (TCF = 2-dicyanomethylene-3-cyano-4-methyl-2,5-dihydrofuran) have been studied by using the ZINDO-SOS method. The results have revealed that OPA and TPA of ferrocenyl derivatives are affected by the strength of the acceptor, especially the pi-bridge conjugation length. The TPA cross section increases with increasing acceptor strength and pi-bridge conjugation length. The TCF-type acceptor with a phenyl group can lead to a larger TPA cross section. Quadrupole molecules have the largest TPA cross sections (2000-3000 GM), which are about 4 times that of the corresponding dipolar molecules, indicating larger interactions between the top and bottom branches. Finally, the origins of the two-photon excitations for ferrocenyl derivatives are analyzed. The calculations show that ferrocenyl derivatives with TCF-type acceptors (especially quadrupole molecules) are promising candidates for TPA materials.