Selective oxidation of β-keto ester modulated by the d-band centers in D-A conjugated microporous metallaphotoredox catalysts containing M-salen (MZn, Cu and Co) and triazine monomers.

Photocatalytic selective oxidation plays an important role in developing green chemistry. However, it is challenging to design an efficient photocatalyst for controlling the selectivity of photocatalytic oxidation reaction and exploring its detailed mechanism. Here, we synthesized three conjugated microporous polymers (CMPs) with D-A structures, named M-SATE-CMPs (MZn, Cu and Co), with different d-band centers based on different metal centers, resulting in the discrepancy in adsorption and activation capacities for the reactants, which produces the selectivity of β-keto esters being catalyzed into α-hydroperoxide β-keto esters (ROOH) or to α-hydroxyl β-keto esters (ROH).

Bisphosphine-Stabilized Gold Nanoclusters with the Crown/Birdcage-Shaped Au Cores: Structures and Optical Properties.

To estimate the effect of bisphosphine ligands on the formation of the isomeric core structures of gold nanoclusters, the different ligation of bisphosphine ligands is usually used to participate in the construction of gold nanoclusters. Here, the selection of the different bisphosphine ligands, DPEphos and Xantphos, is performed to construct two novel gold nanoclusters, [Au(DPEphos)Cl]Cl () and [Au(Xantphos)Cl]Cl(), which have been characterized by IR, H and P NMR, ESI-MS, XRD, SEM, XPS, TG, UV-vis, and X-ray crystal structure analysis. The structural analyses indicate that the ligation of bisphosphine ligands play a crucial role in the formation of the fascinating Au cores: gold nanocluster includes a birdcage-shaped Au core with eight electrons, while gold nanocluster contains a crown-shaped Au core with eight electrons.

Synthesis, structural characterization and luminescent properties of a series of Cu(I) complexes based on polyphosphine ligands.

A series of Cu(I) complexes with a [Cu(NN)(PP)](+) moiety, [Cu(phen)(pba)](BF(4)) (1a), [Cu(2)(phen)(2)(pbaa)](BF(4))(2) (2a), [Cu(2)(phen)(2)(pnaa)](BF(4))(2) (3a), [Cu(2)(phen)(2)(pbbaa)](BF(4))(2) (4a), [Cu(dmp)(pba)](BF(4)) (1b), [Cu(2)(dmp)(2)(pbaa)](BF(4))(2) (2b), [Cu(2)(dmp)(2)(pnaa)](BF(4))(2) (3b) and [Cu(2)(dmp)(2)(pbbaa)](BF(4))(2) (4b) (phen = 1,10-phenanthroline, dmp = 2,9-dimethyl-1,10-phenanthroline, pba = N,N-bis((diphenylphosphino)methyl)benzenamine, pbaa = N,N,N',N'-tetrakis((diphenylphosphino)methyl)benzene-1,4-diamine, pnaa = N,N,N',N'-tetrakis((diphenylphosphino)methyl)naphthalene-1,5-diamine and pbbaa = N,N,N',N'-tetrakis((diphenylphosphino)methyl)biphenyl-4,4'-diamine), were rationally designed and synthesized. These complexes were characterized by (1)H and (31)P NMR, electrospray mass spectrometry, elemental analysis and X-ray crystal structure analysis. Introduction of different central arene spacers (phenyl, naphthyl, biphenyl) into ligands, resulting in the size variation of these complexes, aims to tune the photophysical properties of the complexes.

Bis{N,N-bis-[(diphenyl-phosphan-yl)meth-yl]aniline-κP,P'}copper(I) tetra-fluoridoborate.

In the cation of the title compound, [Cu(C(32)H(29)NP(2))(2)]BF(4), the Cu(I) atom is four-coordinated in a distorted tetra-hedral geometry by four P atoms from two N,N-bis-[(diphenyl-phosphan-yl)meth-yl]aniline ligands. In the crystal, the cations are linked by C-H⋯π inter-actions, forming chains along the a axis. Intra-molecular C-H⋯N and inter-molecular C-H⋯F hydrogen bonds are also observed.

Bis[4-(2-hydroxy-benzyl-ideneamino)benzoato-κO]tetrakis-(methanol-κO)manganese(II).

In the title mononuclear complex, [Mn(C(14)H(10)NO(3))(2)(CH(3)OH)(4)], the Mn(II) atom, lying on an inversion centre, exhibits a distorted octa-hedral geometry, defined by two O atoms from two monodentate ligands and four O atoms from four methanol mol-ecules. The crystal structure involves intra-molecular O-H⋯N and O-H⋯O and inter-molecular O-H⋯O hydrogen bonds.

{μ-trans-N,N'-Bis[(diphenyl-phosphan-yl)meth-yl]benzene-1,4-diamine-κP:P'}bis-{(acetonitrile-κN)[dipyrido[3,2-a:2',3'-c]phenazine-κN,N]copper(I)} bis-(tetra-fluoridoborate).

In the centrosymmetric dinuclear title compound, [Cu(2)(C(2)H(3)N)(2)(C(18)H(10)N(4))(2)(C(32)H(30)N(2)P(2))](BF(4))(2), the Cu(I) centre is coordinated by two N atoms from a dipyridophenazine ligand, one P atom from an N,N'-bis-[(diphenyl-phosphan-yl)meth-yl]benzene-1,4-diamine (bpbda) ligand, and one N atom from an acetonitrile mol-ecule in a distorted tetra-hedral geometry. The bpbda ligand, lying on an inversion center, bridges two Cu(I) centres into a Z-shaped complex. Intra-molecular π-π inter-actions between the dipyridophenazine ligand and the benzene ring of the bpbda ligand are observed [centroid-centroid distance = 3.