Stereochemically Active and Inactive Lone Pairs in Two Room-Temperature Phosphorescence Coordination Polymers of Pb2+ with Different Tricarboxylic Acids.

Two new Pb2+-based coordination polymers (CPs), [Pb2(HBTC)2(DMF)] (1) and [Pb(HPTC)] (2), have been synthesized under solvothermal condition; herein, H3BTC and H3PTC represent 1,3,5-benzenetricarboxylic acid and 2,4,6-pyridine tricarboxylic acid, respectively. Both 1 and 2 were characterized by microanalysis, infrared spectra (IR), thermal gravimetric analyses (TGA), and powder X-ray diffraction (PXRD) techniques. Single-crystal structural analysis indicates that 1 and 2 show different coordination sphere around Pb2+ ions and distinct coordination frameworks. The I1O2 type three-dimensional (3D) nonporous metal-organic framework forms in 1, where the Pb2+ ion shows holo-directed coordination geometry, while the I0O2 type two-dimensional (2D) coordination polymeric layered structure forms in 2, where Pb2+ ion shows a hemidirected coordination sphere and the 6s2 lone electron pair in Pb2+ ion is stereochemically active. The two CPs emit intense and long-lasting greenish phosphorescence in air at room temperature, with absolute quantum yields of 1.2% for 1 and 4.7% for 2 and decay lifetimes of 0.73 ms for 1 and 1.52 ms for 2.

Nearly Pure Red Color Upconversion Luminescence of Ln-Doped Sc2O3 with Unexpected RE-MOFs Molecular Alloys as Precursor.

Unexpected Sc/Ln codoped rare earth metal-organic frameworks (RE-MOFs) molecular alloys (MAs) based on an oxalic acid ligands were obtained. Calcination of the RE-MOFs MAs gave the corresponding codoped rare earth oxides a strong and nearly pure red color upconversion luminescence. It allows the resulting lanthanide ion (Ln3+) doped upconversion materials a wide range of applications from optical communications to disease diagnosis. Moreover, the pyrolysis RE-MOFs MAs precursor has demonstrated to be an effective preparation method for a uniform Ln-doped Sc2O3 system.

Prussian blue analogue derived from leather waste as a bifunctional catalyst in zinc-air batteries.

A Prussian blue analogue was synthesized using biomass leather waste as a precursor by doping with Co2+ ions. This material, demonstrates good performance in both the oxygen reduction reaction and oxygen evolution reaction, and exhibits excellent charge-discharge performance and stability in zinc-air batteries.

Stack pattern of the countercation-modulating magnetic property of low-dimensional [Pt(mnt)2]⁻ monoanion spin systems.

Three [1-N-(4'-R-benzyl)-4-aminopyridinium][Pt(mnt)(2)] compounds were structurally and magnetically characterized, where the substituent was attached to the para-position of the phenyl ring (R = CN (1), Cl (2), and H (3); mnt(2-) = maleonitriledithiolate). 1 and 2 crystallized in the monoclinic space group P2(1)/c, with the cations and anions forming segregated columnar stacks. Their structural differences involved two aspects: (1) both anion and cation stacks were regular in 1 and irregular in 2; (2) the neighboring cations were arranged in the boat-type pattern in 1, whereas these cations were in the chair-type pattern in 2 within the cation stack. 3 belonged to the triclinic space group P ̅1, where the anions were assembled into the stack with a tetrameric [Pt(mnt)(2)](-) subunit, but the cations did not form the columnar stack. Magnetic measurements disclosed that a spin-Peierls-type transition occurred around 240 K for 1, whereas a long-range, antiferromagnetic ordering took place at about 5.8 K, and a metamagnetic phenomenon was observed with H(C) ≈ 1000 Oe for 2; 3 showed very strong antiferromagnetic interactions with diamagnetism in the temperature range 5-300 K. Combined with our previous studies, the correlation between the stacking pattern of benzylpyridinium derivatives in a cation stack and the spin-Peierls-type transition is discussed for the series of quasi-1-D [M(mnt)(2)](-) (M = Ni, Pd and Pt) compounds.

Bis(3,5,7-triaza-1-azoniatricyclo-[3.3.1.1]deca-ne) bis-(1,2-dicyano-ethene-1,2-dithiol-ato)nickelate(II).

The asymmetric unit of the title complex, (C(6)H(13)N(4))(2)[Ni(C(4)N(2)S(2))(2)], comprises one 1-azonia-3,5,7-triaza-tricyclo-[3.3.1.1(3,7)]decane cation and one half of an [Ni(mnt)(2)](2-) (mnt(2-) is maleonitrile-dithiol-ate or 1,2-dicyano-ethene-1,2-dithiol-ate) dianion. The Ni(2+) ion is located on a center of inversion and is coordinated by four S atoms from two mnt(2-) ligands in a square-planar coordination mode. Inter-molecular N-H⋯N hydrogen-bond inter-actions link one anion and two cations in the crystal structure.

Bis[1-(4-cyano-benz-yl)pyrazinium] bis-(1,2-dicyano-ethene-1,2-dithiol-ato)nickelate(II).

The asymmetric unit of the title complex, (C(12)H(10)N(3))(2)[Ni(C(4)N(2)S(2))(2)], consists of one 1-(4-cyano-benz-yl)pyrazinium cation and one half of an [Ni(mnt)(2)](2-) dianion (mnt(2-) is 1,2-dicyano-ethene-1,2-dithiol-ate). The Ni(2+) ion is located on an inversion center and is coordinated by four S atoms from two mnt(2-) ligands, exhibiting a square-planar coordination geometry. The cation adopts a conformation where both the pyrazine ring and the benzene ring are twisted with respect to the C-C-N reference plane by 16.5 (2) and 69.8 (1)°, respectively.

Co3O4 nanoparticles embedded in nitrogen-doped graphitic carbon fibers as a free-standing electrode for promotion of lithium ion storage with capacitive contribution.

Here, we wrap Co3O4 nanoparticles with nitrogen-doped graphitic carbon nanofibers (Co3O4@NGFs) as a self-standing electrode for lithium-ion batteries. In this structure, graphitic carbon acts as a composite framework that enhances conductivity, accommodates volume expansion and increases contact with the electrolyte. Meanwhile, the porosity of Co3O4@NGFs not only facilitates rapid electron transfer, but also exposes more active sites for lithium storage.

Crystal Structures, Photoluminescence, and Magnetism of Two Novel Transition-Metal Complex Cocrystals with Three-Dimensional H-Bonding Organic Framework or Alternating Noncovalent Anionic and Cationic Layers.

Cocrystallization may alter material physicochemical properties; thus, the strategy of forming a cocrystal is generally used to improve the material performance for practical applications. In this study, two transition-metal complex cocrystals [Zn(bpy)3]H0.5BDC·H1.5BDC·0.5bpy·3H2O (1) and [Cu2(BDC)(bpy)4]BDC·bpy·2H2O (2) have been achieved using a hydrothermal reaction, where bpy and H2BDC represent 2,2'-bipyridine and benzene-1,3-dicarboxylic acid, respectively. Cocrystals were characterized by microanalysis, infrared spectroscopy, and UV-visible spectroscopy. Cocrystal 1 contains five components and crystallizes in a monoclinic space group P21/n. The H0.5BDC1.5-, H1.5BDC0.5-, and H2O molecules construct three-dimensional H-bonding organic framework; the [Zn(bpy)3]2+ coordination cations and uncoordinated bpy molecules reside in channels, where two coordinated bpy ligands in [Zn(bpy)3]2+ and one uncoordinated bpy adopt sandwich-type alignment via π···π stacking interactions. Cocrystal 2 with four components crystallizes in a triclinic space group P-1 to form alternating layers; the binuclear [Cu2(bpy)4(BDC)]2+ cations and uncoordinated bpy molecules build the cationic layers, and the BDC2- species with disordered lattice water molecules form the anionic layers. Cocrystal 1 shows intense photoluminescence at an ambient condition with a quantum yield of 14.96% and decay time of 0.48 ns, attributed to the π* → π electron transition within phenyl/pyridyl rings, and 2 exhibits magnetic behavior of an almost isolated spin system with rather weak antiferromagnetic coupling in the [Cu2(bpy)4(BDC)]2+ cation.

NaF-mediated controlled-synthesis of multicolor Na(x)ScF(3+x):Yb/Er upconversion nanocrystals.

Synthesis of lanthanide-doped upconversion nanocrystals (LDUNs) with controlled morphology and luminescence has long been desired in order to fulfill various application requirements. In this work, we have investigated the effect of the NaF : Ln(3+) molar ratio, in the range of 1 to 20, on the morphology, crystal structure, and upconversion properties of NaxScF(3+x):Yb/Er nanocrystals that are reported to possess different upconversion properties from those of NaYF4:Yb/Er nanocrystals. The experimental results prove that the NaF : Ln(3+) molar ratio influences significantly the growth process of the nanocrystals, i.e. a low NaF : Ln(3+) molar ratio results in hexagonal NaScF4 nanocrystals, while a high NaF : Ln(3+) molar ratio favors monoclinic Na3ScF6 nanocrystals. When the NaF : Ln(3+) molar ratio is as high as 6 or above, phase separation is found and hexagonal NaYbF4 nanocrystals showed up for the first time. Simply by adjusting the NaF : Ln(3+) molar ratio, we have successfully achieved the simultaneous control of the shape, size, as well as the crystallographic phase of the NaxScF(3+x):Yb/Er nanocrystals, which give different red to green (R/G) ratios (integral area), leading to a multicolor upconversion luminescence from orange-red to green. This study provides a vivid example to track and interpret the formation mechanisms and growth processes of NaxScF(3+x):Yb/Er nanocrystals, which shall be instructive for guiding the controlled synthesis of other LDUNs and extending their according applications in optical communication, color display, anti-counterfeiting, bioimaging, and so on.

Observation of metal ion dependent packing structures and magnetic behaviors of metal-bis-1, 2-dithiolene complexes.

The crystal structures and magnetic properties were investigated experimentally and theoretically for two S = ½ spin chain complexes, which consist of [M(mnt)(2)](-) (M = Pt for 1 or Pd for 2) with 1-(4'-bromo-2'-flurobenzyl)-4-aminopyridinium (1-BrFBz-4-NH(2)Py(+)). The 1-BrFBz-4-NH(2)Py(+) cations exhibit different molecular conformations and arrangements in 1 and 2; the [M(mnt)(2)](-) anions form regular stacks in 1, whereas they form irregular stacks in 2. In addition, the intermolecular interactions between the [M(mnt)(2)](-) anions and cations are also different from each other in the crystals of 1 and 2. Complex 1 shows the magnetic characteristics of a low-dimensional antiferromagnetic coupling spin system with a spin-Peierls-type transition around 7 K, and complex 2 exhibits diamagnetism over the temperature range of 5-300 K. Theoretical analyses, based on the calculations for the charge density distributions of [Pt(mnt)(2)](-) and [Pd(mnt)(2)](-) anions and the magnetic exchange constants within the anion spin chains, addressed the diverse molecular alignments in the crystals of 1 and 2 and distinct magnetic behaviors between 1 and 2.

Observation of divergent isotope effects as well as metal ion-modulated T(C) and spin-canting nature in isostructural supramolecular magnets.

The ion-pair complexes of [4-NH(2)-PyH][M(mnt)(2)] (M = Pt for 1 and Ni for 3) and their deuterated analogues [4-NH(2)-PyD][M(mnt)(2)] (M = Pt for 2 and Ni for 4) are isostructural with each other. Four complexes crystalline in monoclinic space group C2/c, whose asymmetric unit consists of two halves of [M(mnt)(2)](-) anions and one cation, show quite similar cell parameters and almost identical packing structures as well. In the crystals of 1-4, two types of crystallographically inequivalent [M(mnt)(2)](-) anions construct individual layers, which are separated by the cation layer; the supramolecular networks are formed via the H-bonding interactions between the [M(mnt)(2)](-) and 4-NH(2)-PyH(+) (or 4-NH(2)-PyD(+)) ions as well as the weakly ππ stacking interactions between the [M(mnt)(2)](-) anions. The four isostructural complexes exhibit canted antiferromagnetism, arising from the non-collinearity of the magnetic moments between the crystallographically inequivalent anion layers, with T(C) ≈ 14.8 K for 1, 13.6 K for 2, 7.7 K for 3 and 8.8 K for 4, respectively. Ac magnetic susceptibility measurements revealed that 1 and 2 show spin canting, while 3 and 4 show hidden-spin canting characteristics. The isostructural 1 and 3 were deuterated to give the divergent isotope effects on the cell volume and T(C).

Ion-pair complexes with strong near infrared absorbance: syntheses, crystal structures and spectroscopic properties.

Three ion-pair complexes, [4-NH(2)-Py](2)[M(mnt)(2)] (4-NH(2)-Py(1+)=4-amino-pyridinium; mnt(2-)=maleonitriledithiolate; M=Pt (1), Pd (2) or Ni (3)), have been synthesized and characterized. In the crystal of 1, the strong H-bonding interaction was found from the protonated N-atom of pyridinium to the CN group of [Pt(mnt)(2)](2-) together with a weak Pt...H interaction between the anion and the cation. The crystals of 2 and 3 are isostructural with very similar lattice parameters and packing structures, which are distinct from the crystal of 1. Two kinds of strong H-bonding interactions are observed in the crystals of 2 and 3 between the CN groups of [M(mnt)(2)](2-) anion and the protonated N-atom of 4-NH(2)-Py(1+) cation as well as the CN groups of [M(mnt)(2)](2-) anion and the amino group of 4-NH(2)-Py(1+) cation. Complex 1 shows an intense near-IR absorbance in acetonitrile and solid state, such an absorption band is probably assigned to IPCT transition as well as a trace amount of [Pt(mnt)(2)](1-) species; complex 3 possesses a weak near-IR absorption band which can be attributed to the mixture of d-d transition in [Ni(mnt)(2)](2-) and IPCT transition as well as a trace amount of [Ni(mnt)(2)](1-) species.