Coordination-directed self-assembly has become a well-established technique for the construction of functional supramolecular structures. In contrast to the most often exploited transition metals, trivalent lanthanides Ln(III) have been less utilized in the design of polynuclear self-assembled structures despite the wealth of stimulating applications of these elements. In particular, stereochemical control in the assembly of lanthanide chiral cage compounds is not easy to achieve in view of the usually large lability of the Ln(III) ions. We report here the first examples of stereoselective self-assembly of chiral luminescent europium coordination tetrahedral cages and their intriguing self-sorting behavior. Two pairs of R and S ligands are designed on the basis of the pyridine-2,6-dicarboxamide coordination unit, bis(tridentate) L1 and tris(tridentate) L2. Corresponding chiral Eu4(L1)6 and Eu4(L2)4 topological tetrahedral cages are independently assembled via edge- and face-capping design strategies, respectively. The chirality of the ligand is transferred during the self-assembly process to give either Δ or Λ metal stereochemistry. The self-assembled cages are characterized by NMR, high-resolution ESI-TOF-MS, and in one case by X-ray crystallography. Strict control of stereoselectivity is confirmed by CD spectroscopy and NMR enantiomeric differentiation experiments. Narcissistic self-sorting is observed in the self-assembly process when two differently shaped ligands L1 and L2 are mixed. More impressively, distinct self-sorting behavior between Eu4(L1)6 and Eu4(L2)4 coordination cages is observed for the first time when racemic mixtures of ligands are used. We envisage that chiral luminescent lanthanide tetrahedral cages could be used in chiroptical probes\sensors and enantioselective catalysis.

Two 2D microporous metal-organic frameworks have been assembled from a fluorophore ligand, whose quantum yields of strong blue emissions could vary from 40.3% to 74.5% and 13.7% to 25.8% with the decreasing temperature.

Three novel coordination polymers, [Cd(5)(HTTHA)(2)(Hpt)(4)(H(2)O)]·4H(2)O (1; H(6)TTHA = 1,3,5-triazine-2,4,6-triamine hexaacetic acid, Hpt = pyridinium-4-thiolate), {[Cd(3)(TTHA)(dps)(H(2)O)(3)](2)}·H(2)O (2), and [Zn(3)(TTHA)(dps)(H(2)O)]·5H(2)O (3; dps =4,4'-dipyridylsulfide), have been synthesized by the flexible hexapodal acid H(6)TTHA and in-situ-generated Hpt and dps ligands from a 4,4'-dipyridyldisulfide (dpds) precursor through cleavage of both S-S and S-C(sp(2)) bonds and temperature-dependent chemical rearrangement under hydrothermal conditions. Polymers 2 and 3 exhibit 3D frameworks, while in 1, the extended 3D network can be described as 2D layers further bridged via H-bond interaction. Intriguingly, the three compounds have shown an unusual luminescence thermochromism. Upon decreasing the temperature from 298 to 10 K, the emission bands grow in intensity and change in color dramatically.

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Four nickel clusters, cyclo-[{Ni(μ-S(i)Pr)(μ-SMe)}(6)] (1), cyclo-[{Ni(μ-StBu)(μ-SMe)}(6)] (2), cyclo-[{Ni(μ-S(i)Pr)(μ-SEt)}(6)] (3) and cyclo-[{Ni(μ-StBu)(μ-SEt)}(10)] (4), based on thiolate ligands have been successfully synthesized and characterized by elemental analysis, FT-IR spectra, UV-vis-NIR spectra, powder X-ray diffraction and single-crystal X-ray diffraction. Intriguingly, the SMe and SEt ligands are generated from solvothermal in situ ligand synthesis through the cleavage of the S-S bond respectively. The four nickel thiolate clusters exhibit tiara-like frameworks consisting of two different types of thiolate ligands.

This study was conducted to examine dietary tea catechins (TC) supplementation on the fatty acid composition of muscle and ruminal bacteria in goats fed a maize stover-based diet. Forty goats, 8 months old (16.2 ± 1.2 kg), were randomly divided into four equal groups (10 animals in each group) and assigned to four experiment diets with TC supplementation at four levels (0, 2,000, 3,000 and 4,000 mg TC/kg feed, namely TC0, TC2000, TC3000 and TC4000, respectively). After a 60-day feeding period, all the goats were slaughtered and sampled. The results showed that dietary TC inclusion increased the average daily gain (ADG), protein content in the semimembranosus muscle and dry matter in the longissimus dorsi muscle (LD). Dietary TC supplementation increased the ratio of n-6 to n-3 fatty acid, the ratio of polyunsaturated fatty acids to saturated fatty acids was higher in TC3000 and TC4000 than in TC0 and TC2000 for LD. The current results implied that dietary inclusion of a suitable TC dose could improve the growth performance and increase the proportions of unsaturated fatty acids in muscle, and the biohydrogenation of ruminal microorganisms might change the profiles of fatty acids in the muscle of growing goats.

The microporous metal-organic framework (MMOF) Zn4O(L1)2⋅9 DMF⋅9 H2O (1-H) and its functionalized derivatives Zn4O(L1-CH3)2⋅9 DMF⋅9 H2O (2-CH3) and Zn4O(L1-Cl)2⋅9 DMF⋅9 H2O (3-Cl) have been synthesized and characterized (H3L1=4-[N,N-bis(4-methylbenzoic acid)amino]benzoic acid, H3L1-CH3=4-[N,N-bis(4-methylbenzoic acid)amino]-2-methylbenzoic acid, H3L1-Cl=4-[N,N-bis(4-methylbenzoic acid)amino]-2-chlorobenzoic acid). Single-crystal X-ray diffraction analyses confirmed that the two functionalized MMOFs are isostructural to their parent MMOF, and are twofold interpenetrated three-dimensional (3D) microporous frameworks. All of the samples possess enduring porosity with Langmuir surface areas over 1950 cm(2) g(-1). Their pore volumes and surface areas decrease in the order 1-H>2-CH3 >3-Cl. Gas-adsorption studies show that the H2 uptakes of these samples are among the highest of the MMOFs (2.37 wt% for 3-Cl at 77 K and 1 bar), although their structures are interpenetrating. Furthermore, this work reveals that the adsorbate-adsorbent interaction plays a more important role in the gas-adsorption properties of these samples at low pressure, whereas the effects of the pore volumes and surface areas dominate the gas-adsorption properties at high pressure.

To investigate how the central metalloligand geometry influences distant or vicinal metal-to-metal charge-transfer (MMCT) properties of polynuclear complexes, cis- and trans-isomeric heterotrimetallic complexes, and their one- and two-electron oxidation products, cis/trans-[Cp(dppe)Fe(II)NCRu(II)(phen)2CN-Fe(II)(dppe)Cp][PF6]2 (cis/trans-1[PF6]2), cis/trans-[Cp(dppe)Fe(II)NCRu(II)(phen)2CNFe(III)-(dppe)Cp][PF6]3 (cis/trans-1[PF6]3) and cis/trans-[Cp(dppe)Fe(III)NCRu(II)(phen)2CN-Fe(III)(dppe)Cp][PF6]4 (cis/trans-1[PF6]4) have been synthesized and characterized. Electrochemical measurements show the presence of electronic interactions between the two external Fe(II) atoms of the cis- and trans-isomeric complexes cis/trans-1[PF6]2. The electronic properties of all these complexes were studied and compared by spectroscopic techniques and TDDFT//DFT calculations. As expected, both mixed valence complexes cis/trans-1[PF6]3 exhibited different strong absorption signals in the NIR region, which should mainly be attributed to a transition from an MO that is delocalized over the Ru(II)-CN-Fe(II) subunit to a Fe(III) d orbital with some contributions from the co-ligands. Moreover, the NIR transition energy in trans-1[PF6]3 is lower than that in cis-1[PF6]3, which is related to the symmetry of their molecular orbitals on the basis of the molecular orbital analysis. Also, the electronic spectra of the two-electron oxidized complexes show that trans-1[PF6]4 possesses lower vicinal Ru(II) → Fe(III) MMCT transition energy than cis-1[PF6]4. Moreover, the assignment of MMCT transition of the oxidized products and the differences of the electronic properties between the cis and trans complexes can be well rationalized using TDDFT//DFT calculations.