Homochiral crystallizations of two enantiomeric metal-organic frameworks (MOFs) Ce-MDIP1 and Ce-MDIP2 were achieved by using L- or D-BCIP as chiral inductions, respectively, where the chiralities were characterized by solid state CD spectra. Ce-MDIPs exhibit excellent catalytic activity and high enantioselectivity for the asymmetric cyanosilylation of aromatic aldehydes; the homochiral Cd-TBT MOF having L-PYI as a chiral adduct exhibits stereochemical catalysis toward the Aldol reactions.

Five novel interesting d(10) metal coordination polymers, [Zn(PDCO)(H2O)2]n (PDCO = pyridine-2,6-dicarboxylic acid N-oxide) (1), [Zn2(PDCO)2(4,4'-bpy)2(H2O)2.3H2O]n (bpy = bipyridine) (2), [Zn(PDCO)(bix)]n (bix = 1,4-bis(imidazol-1-ylmethyl)benzene) (3), [Zn(PDCO)(bbi).0.5H2O]n (bbi = 1,1'-(1,4-butanediyl)bis(imidazole)) (4), and [Cd(PDCO)(bix)(1.5).1.5H2O]n (5), have been synthesized under hydrothermal conditions and structurally characterized. Polymer 1 possesses a one-dimensional (1D) helical chainlike structure with 4(1) helices running along the c-axis with a pitch of 10.090 Angstroms. Polymer 2 has an infinite chiral two-dimensional (2D) brick-wall-like layer structure in the ac plane built from achiral components, while both 3 and 4 exhibit an infinite 2D herringbone architecture, respectively extended in the ac and ab plane. Polymer 5 features a most remarkable and unique three-dimensional (3D) porous framework with 2-fold interpenetration related by symmetry, which contains channels in the b and c directions, both distributed in a rectangular grid fashion. Compounds 1-5, with systematic variation in dimensionality from 1D to 2D to 3D, are the first examples of d(10) metal coordination polymers into which pyridinedicarboxylic acid N-oxide has been introduced. In addition, polymers 1, 4, and 5 display strong blue fluorescent emissions in the solid state. Polymer 3 exhibits a strong SHG response, estimated to be approximately 0.9 times that of urea.

Two 2:2 types of monolanthanide substituted polyoxometalates [{(R-PW 11 O 39 H)Ln(H 2 O) 3 } 2 ] 6-(Ln=Nd III for 1 and Gd III for 2) and [{(R-PW 11 O 39 )Ln(H 2 O)(η 2 ,μ-1,1)-CH 3 COO} 2 ] 10-(Ln=Sm III for 3, Eu III for 4, Gd III for 5, Tb III for 6, Ho III for 7 and Er III for 8) have been synthesized in aqueous solution and characterized by elemental analyses, IR spectra, UV-vis-NIR spectra, thermogravimatric analyses and single-crystal X-ray diffraction. The common structural features are that they are constructed from monovacant Keggin-type polyoxoanions [R-PW 11 O 39 ] 7and trivalent lanthanide cations. Both 1 and 2 are essentially isomorphous, and the molecular structure is built by two symmetrically related monolanthanide substituted Keggin units [R-PW 11 O 39 Ln(H 2 O) 3 ] 4linked via two Ln-O-W bridges, representing the first monovacant Keggin polyoxotungstate dimers constituted by two [R-PW 11 O 39 ] 7polyoxoanions and two lanthanide cations in polyoxometalate chemistry. 3-8 are also isostructural and display another dimeric structure constructed from two monolanthanide substituted units [(R-PW 11 O 39 )Ln(H 2 O)(η 2 ,μ-1,1)-CH 3 COO] 5bridged by two (η 2 ,μ-1,1)-acetato ligands. The photoluminescence properties of 4 and 6 were investigated at room temperature. Magnetic susceptibility measurements of 1, 3, 4, 7 and 8 between 2 and 300 K exhibit that their magnetic behaviors mainly result from the spin-orbital coupling interactions as well as weak antiferromagnetic exchange interactions within magnetic centers. The electrochemical properties of 1, 3, 4, 5, 7 and 8 were studied by means of cyclic voltammetry in aqueous solution with 0.5 M Na 2 SO 4 as supporting electrolyte.

The incorporation of oxygen vacancy defects into the catalysts has been attracting significant interest for regulating the performance of photocatalysts. Single-atomic-site metal catalysts have also been paid ever-growing attention because they maximized the atom efficiency and thus generated excellent catalytic performance. Herein, we report the interaction of oxygen vacancy defects and decorated atomically dispersed metal Pt to boost the efficient photocatalytic process. Compared with TiO2 without oxygen defects, under the same theoretical amount of Pt support, all the oxygen vacancy defect-rich TiO2 catalysts show excellent photocatalytic H2 generation and CO2 reduction performance. On the basis of the experimental characterization and quantum chemical calculations, the introduced oxygen vacancies strongly anchored the single-atom Pt on the surface of the catalyst with enhanced Pt-substrate interactions and thereby avoiding aggregation of Pt atoms, while the loaded single Pt atom favor the generation of more surface and subsurface oxygen vacancies as proved by electron spin resonance and positron annihilation lifetime spectroscopy. This work represents a new heuristic research of the coeffect of the defects and supported single noble metal atom and the rational synthesis of high-efficiency photocatalysts.