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[Display omitted] Mass cytometry (MC) is an emerging bioanalytical technique for high-dimensional biomarkers interrogation simultaneously on individual cells. However, the sensitivity and multiplexed analysis ability of MC was highly restricted by the current metal chelating polymer (MCP) mass tags. Herein, a new design strategy for MC mass tags by using a commercial available and low cost classical material, polystyrene nanoparticle (PS-NP) to carry metals was reported. Unlike inorganic materials, sub-micron-grade metal-loaded polystyrene can be easily detected by MC, thus it is not essential to pursue extremely small particle size in this mass tag design strategy. An altered cell staining buffer can significantly lower the nonspecific binding (NSB) of non-functionalized PS-NPs, revealing another method to lower NSB beside surface modification. The metal doped PS-NP_Abs mass tags showed high compatibility with MCP mass tags and 5-fold higher sensitivity. By using Hf doped PS-NP_Abs as mass tags, four new MC detection channels (177Hf, 178Hf, 179Hf and 180Hf) were developed. In general, this work provides a new strategy in designing MC mass tags and lowering NSB, opening up possibility of introducing more potential MC mass tag candidates. [ABSTRACT FROM AUTHOR]

Two 3d–4f heterometal–organic frameworks are synthesized by a steam-assisted conversion method and are characterized by single-crystal X-ray diffraction, PXRD, IR, TG, and UV–vis spectroscopy. Compounds 1 and 2 have similar structures, in which binuclear gadolinium clusters are connected by [M(BPDC)3] (M = Ni for 1 and Co for 2) secondary building units (SBUs) and extend into 3D frameworks with pcu topologies. In addition, we have also investigated the photoreduction of CO2 under visible light. The CO yields reached 7622 μmol−1 g−1 and 11 250 μmol−1 g−1 with 1 and 2 as catalysts, respectively, and ruthenium pyridine as the photosensitizer after two hours of visible light irradiation. Both of them have high selectivity values for CO, reaching 94.85% for 1 and 94.46% for 2. Furthermore, the catalytic mechanism is proposed through a photoelectrochemical test. This study provides a feasible strategy for the design of efficient CO2 photocatalysts with a high charge separation rate. [ABSTRACT FROM AUTHOR]

Self‐assembly of transition metal ions with different N‐donor ligands and 3,3′‐azodibenzoic acid (3,3′‐H2ADB) yielded five novel metal‐organic frameworks. All the 3,3′‐ADB2– anions got oxidized into 3,3′‐AO2DB2– and 3,3′‐AODB2– under solvothermal conditions. Compound 1 has a 3D 6‐connected pcu architecture based on [Mn3(COO)6] SBU. Compound 2 exhibits 3D threefold interpenetrating framework based on paddlewheel [Mn2(COO)4] SBU with 41263 topological configuration. Compound 3 bears zigzag double chains, which are then connected by π–π stacking interactions into 2D porous structure. Compound 4 features 2D network with self‐penetrating feature. Compound 5 exhibits a fivefold interpenetrating architecture with dia type. Magnetic measurements show that 1, 2 and 5 exhibit antiferromagnetic behavior. In addition, compound 3 displays significant adsorption towards methylene blue in aqueous solution. Thermogravimetric analyses for 1–5 and the luminescence properties of 3 and 4 have also been investigated. [ABSTRACT FROM AUTHOR]

Solvothermal reactions of 3,3′,5,5′-biphenyltetracarboxylic acid (H4BPTC) and cobalt(ii) ions in the presence of two different flexible N-donor ancillary ligands afford two novel coordination polymers, {[Co(BPTC)0.5(bix)] · H2O} n (1), {[Co(BPTC)0.5(bpp)]·3H2O} n (2) (bix = 1,4-bis(imidazol-1-ylmethyl)benzene; bpp = 1,3-bis(4-pyridyl)propane). Their structures have been determined by elemental analyses, IR spectra, single-crystal X-ray diffraction analyses, and powder X-ray diffraction. The pillared layered framework of 1 can be simplified to a (4,6)-connected net with a Schläfli symbol of (44·62)(44·69·82). Complex 2 manifests a bilayered structure, and can be simplified to a (4,4)-connected net with a Schläfli symbol of (55·8)(54·62). The thermal stabilities of both complexes and the magnetic behaviours of 1 are also discussed. Solvothermal reactions of aromatic 3,3′,5,5′-biphenyltetracarboxylic acid and flexible N-donor ancillary ligands afford two novel coordination polymers. 3D pillar-layered 1 and bilayered 2 can be simplified as a (4,6)- and (4,4)-connected net, respectively. Their thermal stabilities and the magnetic behaviour of 1 are also discussed. [ABSTRACT FROM AUTHOR]

Self-assembly of zinc(II) coordination polymers have attracted intense interests due to their intriguing frameworks and fluorescence properties. Two new 3D ZnII coordination polymers with pcu networks, formulated by [Zn2L1L2(mbtz)] ·H2O ( 1) and [Zn4L12L22(btp)2] ·7H2O ( 2) [H2L1 = 2,5-dibenzoylterephthalic acid, H2L2 = 4,6-dibenzoylisophthalic acid, mbtz = 1,3-bis(1,2,4-triazol-1-ylmethyl)benzene, and btp = 1,3-bis(1,2,4-triazol-1-yl)propane], were synthesized under normal hydrothermal conditions. Single-crystal X-ray diffraction analyses revealed that both of the two compounds exhibited interesting 3D pcu frameworks, and showed shifted fluorescent emissions arising from the coordination chemistry between ZnII and the N-donor ligands. [ABSTRACT FROM AUTHOR]

Two new metal-organic frameworks (MOFs) namely, [Cd (nds) (bimh) 2 ·(bimh)] n (1) and [Cd (nds) (bimb) 2 ] n (2), (nds ​= ​2,6-naphthalenedisulfonate; bimh ​= ​1,6-bis-(imidazole-1-yl)-hexane; bimb ​= ​1,1'-(1,4-butanediyl)bis(imidazole)), have been hydrothermally synthesized. These complexes were characterized by IR spectroscopy, elemental analysis and X-ray single-crystal diffraction. Complex 1 possesses a 3D framework with 6-connected (412.63) pcu topology. Complex 2 shows a 2D layer with Schläfli symbol of (36) (46) (53). The adjacent layers are stacked offset with respect to each other, in an ABAB fashion. Both complexes 1 and 2 exhibit low detection limit and high selectivity toward Cu2+ through the luminescent quenching experiments. Further, the adsorption experiments indicate that complex 1 could efficiently remove I 2 from the cyclohexane solution after 20 ​h with an adsorption capacity of 148.5 ​mg/g. [Display omitted] • Two new Cd-MOFs have been hydrothermally synthesized. • Both complexes 1 and 2 exhibit low detection limit and high selectivity toward Cu2+ in aqueous solution. • Complex 1 could efficiently remove I 2 from the cyclohexane solution. [ABSTRACT FROM AUTHOR]

Molecular self-assembly has played an important role in nanofabrication. Due to the weak driving forces of noncovalent bonds, developing molecular nanoassemblies that have both robust preparation conditions and stable structure is a challenge. In our previous work, we have developed a reversible self-assembly system of Au(I)-thiolate coordination polymer (ATCP) to form colloidal lamellar sheets and demonstrated the high tailorability and stability of their structures, as well as their promising applications in gold nanocluster/nanoparticle fabrication and UV light shielding. Here, we first reported our progress in exploring a robust and green assembly protocol toward ATCP colloidal lamellar sheets in water by allowing the molecular precursors of HAuCl4 and the thiol ligand to form ATCP preassembled intermediates. In this way, colloidal ATCP lamellar sheets can be prepared in a wide range of synthetic concentrations ([Au]0 ≥ 2 × 10-4 M) and at broad assembly temperatures (80-100 °C) with similar high yields (>80%). The assembly kinetics at different conditions are also studied in detail to help understand the robust assembly process. The robust and green synthetic protocols will pave a way for their real applications. [ABSTRACT FROM AUTHOR]

Herein, a series of ionic mononuclear Cu(I) complexes, [Cu(phen)(bdppmapy)]Cl (1a), [Cu(phen)(bdppmapy)]Br (2a), [Cu(phen)(bdppmapy)]I (3a), [Cu(phen)(bdppmapy)]SCN (4a), [Cu(Dpq)(bdppmapy)]Cl (1b), [Cu(Dpq)(bdppmapy)]Br (2b), [Cu(Dpq)(bdppmapy)]I (3b) and [Cu(Dpq)(bdppmapy)]SCN (4b) {phen = [1,10]phenanthroline; Dpq = pyrazino[2,3-f][1,10]-phenanthroline; bdppmapy = N,N-bis((diphenylphosphino)methyl)-2-pyridinamine} have been synthesized and characterized by using IR, NMR, elemental analysis, single crystal X-ray diffraction analysis, fluorescence spectroscopy methods, and UV-vis and terahertz (THz) time-domain absorption spectroscopy. Their crystal structures were elucidated by X-ray crystallography and their photophysical properties were investigated in detail. All the above complexes exhibit a 1D to 3D supramolecular structure which is linked together by intermolecular weak interaction forces and hydrogen bonds. By regulating ligands and anions, the emission wavelengths of these complexes are quite different in the range from 533 nm to 604 nm. Theoretical calculations and photophysical properties indicate that luminescence is derived from metal-to-ligand charge transfer (MLCT) excited states. In the meantime, the results of calculations show that the stabilization of the increased conjugation of the ligand-based π* orbital is ascribed to the observed bathochromic-shift in the MLCT transitions. [ABSTRACT FROM AUTHOR]

[Display omitted] • The different coordination environments can significantly affect the process of OER and ORR of the novel NiN 2. • C 3 /V N3 -NiN 2 and Co/V Ni -NiN 2 systems act as bifunctional OER and ORR catalysts. • The effects of different coordination environments on the origin of OER/ORR activities of the novel NiN 2. For renewable and environment-friendly green energy, it is crucial to look for prominent bifunctional oxygen electrocatalysts. Herein, by doping a single transition metal (TM) or non-metal atom into the two-dimensional NiN 2 to regulate the coordination environment, the electrocatalytic performance is comprehensively studied based on the density functional theory (DFT). By which, we found that catalytic activity could be significantly improved. Specifically, the Co/V Ni -NiN 2 and C 3 /V N3 -NiN 2 systems possess low overpotentials for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) (η OER = 0.38, 0.30 V and η ORR = 0.37, 0.37 V), separately, displaying outstanding bifunctional catalytic activity. The electronic structures of the catalyst system have been investigated to explain the origin of high OER and ORR activities. In addition, this research confirms that the electronegativity of the TM atoms, the d-band center (ε d), and the quantity of d-orbital electrons are reliable descriptors for these TM/V Ni -NiN 2 systems. Thus, this study can serve as guidance for the development of more effective oxygen-catalyzed bifunctional electrocatalysts. [ABSTRACT FROM AUTHOR]

By employing 5-(pyridin-3-yl)-1H-pyrazole-3-carboxylic acid ligand, a new coordination polymer [Cd(HPPC−)2(H2O)2]n (1) has been prepared via the one-pot solvothermal reation with CdI2 and structurally characterized via elemental analysis, FT-IR spectroscopy, single-crystal X-ray diffraction analysis and X-ray powder diffraction. The results represented that 1 is a three-dimensional (3D) framework based on the 2D corrugated layers and Cd–O pillars, which can be considered as a (3,6)-connected trl topology with Schläfli symbol of {4·62}2{42·610·83}. In this work, the photoluminescence and electrogenerated chemiluminescence (ECL) behavior of complex 1 were investigated and thermal stability was confirmed by TGA analysis. Meanwhile, the Brunauer–Emmett–Teller measurement of 1 was also conducted to address the porosity of this 3D structure. Complex 1 exhibited high intense ECL in dimethyl sulfoxide and after eight circulations the ECL efficiency still remained stable, thus providing the possibility for construction of potential polymers ECL materials. In addition, Hirshfeld surface analysis for 1 mapped with various functions and 2D fingerprint plots revealed that the H···H and O···H contacts outnumbered the other contacts in 1 (25.3% and 23.0% of the total interactions, respectively). [ABSTRACT FROM AUTHOR]

Five novel mononuclear [Cu(Bphen)(bdppmapy)]X complexes showing photoluminescence were synthesized. The same diphosphine ligand and diimine ligand and different Cu(I) salts were used in the one-pot synthesis of complexes 1–5. These complexes are listed as follows: [Cu(Bphen)(bdppmapy)]CF3SO3 (1), [Cu(Bphen)(bdppmapy)]BF4·0.268CH3OH (2), [Cu(Bphen)(bdppmapy)]ClO4 (3), [Cu(Bphen)(bdppmapy)]I·CH3OH (4) and [Cu(Bphen)(bdppmapy)]Br·2CH3OH (5) (Bphen = 4,7-diphenyl-1,10-phenanthroline, bdppmapy = N,N-bis((diphenylphosphino)methyl)-2-pyridinamine). IR, NMR, elemental analysis, single-crystal X-ray diffraction analysis, UV-vis, fluorescence spectroscopy and terahertz time-domain absorption spectroscopy (THz-TDS) were used to characterize 1–5. Their crystal structures have been elucidated by X-ray crystallography and their photophysical properties have been investigated in detail. These five complexes have a similar coordination center, while their space stacked structures are different, from a 0D dimeric structure to a 3D supramolecular structure. Photophysical studies and density functional theory calculations (DFT) show that the luminescence properties of these five complexes are mainly ascribed to metal-to-ligand charge transfer (MLCT). Among these five complexes, 1 emits luminescence with the highest quantum yield of 36.96% and a lifetime of 11.90 μs at ambient temperature. Different counter-anions lead to the distinction of QYs, maybe due to the influence of weak forces. Terahertz time-domain absorption spectroscopy was used to characterize these ligands and complexes in the range of 0.2–2.4 THz. [ABSTRACT FROM AUTHOR]

In acidic solution, a serials of water-soluble coordination polymers (CPs) were isolated as zonal 1D-CPs 1,3-propanediaminetetraacetato lanthanides [ Ln (1,3-H 3 pdta)(H 2 O) 5 ] n ·2Cl n ·3 n H 2 O [ Ln =La, 1 ; Ce, 2 ; Pr, 3 ; Nd, 4 ; Sm, 5 ] (1,3-H 4 pdta=1,3-propanediaminetetraacetic acid, C 11 H 18 N 2 O 8 ) in high yields. When 1 eq. mol potassium hydroxide was added to the solutions of 1D-CPs, respectively, two 1D-CPs [Ln(1,3-H 2 pdta)(H 2 O) 3 ] n ·Cl n ·2 n H 2 O [ Ln =Sm, 6 ; Gd, 7 ] were isolated at room temperature and seven 2D-CPs [ Ln (1,3-H 2 pdta)(H 2 O) 2 ] n ·Cl n ·2 n H 2 O [ Ln =La, 8 ; Ce, 9 ; Pr, 10 ; Nd, 11 ; Sm, 12 ; Eu, 13 ; Gd, 14 ] were isolated at 70 °C. When the crystals of 1–4 were hydrothermally heated at 180 °C with 1–2 eq. mol potassium hydroxide, four 3D-CPs [ Ln (1,3-Hpdta)] n · n H 2 O [ Ln =La, 15 ; Ce, 16 ; Pr, 17 ; Nd, 18 ] were obtained. The two 2D-CPs [ Ln (1,3-Hpdta)(H 2 O)] n ·4 n H 2 O (Sm, 19 ; Eu, 20 ) were isolated in similar reaction conditions. With the increments of pH value in the solution and reaction temperature, the structure becomes more complicated. 1–5 are soluble in water and 1 was traced by solution 13 C{ 1 H} NMR technique, the water-soluble lanthanides 1 and 5 show catalytic activity to ester hydrolysis reaction respectively, which indicate their important roles in the hydrolytic reaction. The europium complexes 13 and 20 show visible fluorescence at an excitation of 394 nm. The structure diversity is mainly caused by the variation of coordinated ligand in different pH values and lanthanide contraction effect. Acidic conditions are favorable for the isolations of lanthanide complexes in different structures and this may helpful to separate different lanthanides. The thermal stability investigations reveal that acidic condition is favorable to obtain the oxides at a lower temperature. [ABSTRACT FROM AUTHOR]

On the basis of the 3-(pyrazin-2-yl)-1H-pyrazole-5-carboxylic acid (H2L) ligand, four new polymers [Cu2(L2−)2] (1), [Zn3(L2−)2(H2O)4Cl2]n (2), [Pb(HL−)Cl]n (3), and {[Ni(L2−)(H2O)]·(H2O)}n (4) have been synthesized under solvothermal conditions. Polymer 1 possesses a discrete (0D) binuclear structure, which is further formed into a three-dimensional (3D) supramolecular structure by hydrogen bonding and π⋯π stacking interactions. Polymers 2 and 3 display one-dimensional (1D) infinite chain structures, which further extend into 3D supramolecular structures through hydrogen bonding interactions. Polymer 4 features two-dimensional (2D) layers which can form a 3D supramolecular architecture via interlayer hydrogen bonds. The ligand in the four polymers adopts different coordination modes for constructing versatile structures. Moreover, luminescence sensing study shows that polymer 2 is a promising luminescent sensor for the detection of Cu2+, Co2+ and Fe3+via drastic luminescence quenching in aqueous solution with high efficiency. The quenching constants KSV for Cu2+, Co2+ and Fe3+ are 6.35 × 103 M−1, 8.70 × 103 M−1 and 1.62 × 104 M−1, respectively. What's more, 1–4 with electrochemical luminescence (ECL) properties show high intensity in N,N-dimethylformamide (DMF) solution and high thermal stability. [ABSTRACT FROM AUTHOR]

A new Cu(II)-based coordination polymer (CP), {[Cu(bpa)(1,3-BDC)(H2O)](DMF)n}n (1), (DMF = dimethylformamide) was synthesized by reaction of the Cu(NO3)2·3H2O with the 3,6-bis(benzimidazol-1-yl)pyridazine (bpa) presence of the isophthalic acid (1,3-H2BDC). Its intracerebral hemorrhage (ICH) protective treatment was assessed and the related mechanism was explored as well. The real time RT-PCR was used to detect the relative expression levels of the ROS related genes, which reflected the intracellular ROS levels in the vascular endothelial cells. Next, the western blotting assay was performed and the inflammatory responses levels in the vascular endothelial cells were evaluated. [ABSTRACT FROM AUTHOR]

[Display omitted] • A novel chiral core–shell composite [Zn 2 (D-Cam) 2 (4,4′-bpy)] n @SiO 2 was prepared by an in-situ growth method. • The [Zn 2 (D-Cam) 2 (4,4′-bpy)] n @SiO 2 -packed exhibited excellent resolution ability towards various racemates. • Positional isomers were well separated on the [Zn 2 (D-Cam) 2 (4,4′-bpy)] n @SiO 2 -packed column. Chiral metal–organic frameworks, an emerging type of chiral porous materials, possess many outstanding characteristics such as high surface area, tunable pore sizes, and good chemical stability. Herein, we prepared a chiral [Zn 2 (D-Cam) 2 (4,4′-bpy)] n @SiO 2 core–shell composite on the SiO 2 -NH 2 microspheres by an in-situ growth method. The prepared [Zn 2 (D-Cam) 2 (4,4′-bpy)] n @SiO 2 -packed column exhibited high-resolution separation of racemic compounds and positional isomers at a low column backpressure (9–12 bar). Twelve pairs of enantiomers including alcohols, amines, epoxides, ketones, and esters were well resolved with sharp peak shapes on the [Zn 2 (D-Cam) 2 (4,4́-bpy)] n @SiO 2 chromatographic column. Compared the separation performance of [Zn 2 (D-Cam) 2 (4,4́-bpy)] n @SiO 2 -packed column and two chromatographic columns (commercial Chiralpak AD-H column and as-prepared SiO 2 -NH 2 column), the [Zn 2 (D-Cam) 2 (4,4′-bpy)] n -packed column and the commercial Chiralpak AD-H column have a good complementarity in chiral separation, and it also offered better separation performance compared to the SiO 2 -NH 2 column for separating positional isomers. The effects of column temperature and analyte mass on the HPLC separation were investigated. Additionally, the [Zn 2 (D-Cam) 2 (4,4́-bpy)] n @SiO 2 packed column has good repeatability and stability for HPLC separation of enantiomers and positional isomers. The relatvive standard deviations (RSDs) for repeated separations of 2,2,2-trifluoro-1-(9-anthryl)ethanol and o , m , p -bromoaniline were less than 0.8 % and 1.2 % for the retention time and peak area, respectively. After continuous use for one month, the RSDs for the retention time and peak area of them were in the range of 1.1–1.3 % and 1.5–1.8 % (inter-day and intra-day, n = 5), respectively. This work also indicates that the chiral MOFs@SiO 2 composites are promising for HPLC separation. [ABSTRACT FROM AUTHOR]

A novel cadmium-based coordination polymer can turn-on detection of NOR and turn-off detection of TCH in water. [Display omitted] • A novel cadmium-based coordination polymer was synthesized by a facile solvothermal method. • The complex 1 can effectively identify norfloxacin (NOR) and nitrofurazone (NFZ) in water. • Rational mechanisms of fluorescence enhancement and fluorescence quenching were investigated. • Good stability of the complex 1 can be recovered and recycled. A mixed-ligand cadmium-based coordination polymer was successfully synthesized by solvothermal method and named {[Cd 3 (L)(bipy)(H 2 O) 3 ]·2H 2 O} n (1) (where L = 3,4-bis(3,5-dicarboxyphenyl)phthalic acid, bipy = 2,2′-bipyridine). Subsequently, complex 1 was characterized by single crystal X-ray diffractometer (SC-XRD), powder X-ray diffractometer (PXRD), Fourier transform infrared (FT-IR) spectroscopy, thermogravimetric analysis (TGA) and fluorescence spectroscopy. Due to the excellent photoluminescence properties of complex 1 , it was used to identify antibiotics in water and it can turn-on detection of norfloxacin in water and also quenched detection of nitrofurazone in water with excellent limit of detection. The mechanism is finally discussed in a rational manner by UV–Visible absorption spectra and density functional theory calculations. [ABSTRACT FROM AUTHOR]

A series of lanthanide coordination polymers LnBTPTA (Ln = Eu, Tb, Eu x Tb 1−x ), was synthesized using a tricarbocylic ligand 4,4′,4′′-(benzene-1,3,5-triyltris(1H-pyrazole-3,1-diyl))tribenzoic acid (H 3 BTPTA). X-ray single crystal analyses reveal that the asymmetric unit cell contains seven crystallographically independent metal ions and seven crystallographically independent ligands which is quite unusual. The 3D framework is comprised of 2D thick layers stacked through van der Waals force, π-π interactions and hydrogen bonding interactions. Eu 0.0316 Tb 0.9684 BTPTA presents a dual-emission of Tb 3+ at 543 nm and Eu 3+ at 617 nm, and the intensity ratio shows an excellent linear relationship with the temperature changing in 25–225 K. The relative sensitivity 0.45–5.12% K −1 is much higher than those have been reported in the same detection range. [ABSTRACT FROM AUTHOR]

The development of smart drug delivery systems to realize controlled drug release for highly specific cancer treatment has attracted tremendous attention. Herein, nanoscale coordination polymers (NCPs) constructed from hafnium ions and bis-(alkylthio) alkene (BATA), a singlet-oxygen responsive linker, are fabricated and applied as nanocarriers to realize light-controlled drug release under a rather low optical power density. In this system, NCPs synthesized through a solvothermal method are sequentially loaded with chlorin e6 (Ce6), a photosensitizer, and doxorubicin (DOX), a chemotherapeutic drug, and then coated with lipid bilayer to allow modification with polyethylene glycol (PEG) to acquire excellent colloidal stability. The singlet oxygen produced by such NCP-Ce6-DOX-PEG nanocomposite can be used not only for photodynamic therapy, but also to induce the break of BATA linker and thus the destruction of nanoparticle structures under light exposure, thereby triggering effective drug release. Notably, with efficient tumor accumulation after intravenous injection as revealed by CT imaging, those NCP-Ce6-DOX-PEG nanoparticles could be utilized for combined chemo-photodynamic therapy with great antitumor efficacy. Thus, this work presents a unique type of NCP-based drug delivery system with biodegradability, sensitive responses to light, as well as highly efficient tumor retention for effective cancer combinational treatment. [ABSTRACT FROM AUTHOR]

A novel two-dimensional zinc-based coordination polymer produces hydroxyl radicals and superoxide radicals in visible light to accelerate the elimination of dyes from water. [Display omitted] A novel two-dimensional zinc-based coordinated polymer was successfully synthesized with the assistance of solvothermal method, which named as {Zn(HL)(H 2 O) 2 } n (1) (Where H 3 L = 4-(2,4-dicarboxylphenyl)picolinic acid). Under visible light, the coordination polymer exhibits excellent photocatalytic properties and can effectively eliminate organic dyes such as rhodamine B (Rh B) and methyl orange (MO) from aqueous solutions. In addition, to explore the photocatalytic mechanism, the radical-active species in the photocatalytic reaction process were analyzed with the assistance of three different radical trapping agents, and the in-depth mechanisms was discussed with the contribution of density functional theory calculations. [ABSTRACT FROM AUTHOR]

Nanoscale coordination polymers (NCPs) self-assembled from metal ions and organic bridging ligands exhibit many unique features promising for applications in nanomedicine. In this work, manganese dioxide (MnO2) nanoparticles stabilized by bovine serum albumin are encapsulated by NCP-shells constructed based on high-Z element hafnium (Hf) ions and c,c,t-(diamminedichlorodisuccinato)Pt(IV) (DSP), a cisplatin prodrug. After further modification with polyethylene glycol (PEG), the formed BM@NCP(DSP)-PEG can simultaneously serve as a radio-sensitizer owing to the strong X-ray attenuation capability of Hf to enhance radiotherapy, as well as a chemotherapeutic agent resulting from the reduction-induced release of cisplatin. Meanwhile, the in situ generated oxygen resulting from MnO2-triggered decomposition of tumor endogenous H2O2 will be greatly helpful for overcoming hypoxia-associated radio-resistance. Upon intravenous injection, BM@NCP(DSP)-PEG shows efficient tumor homing as well as rapid renal excretion, as illustrated by magnetic resonance imaging and confirmed by biodistribution measurement. Notably, an excellent in vivo tumor growth inhibition effect is observed with BM@NCP(DSP)-PEG nanoparticles after the combined chemoradiotherapy treatment. Therefore, the NCP-based composite nanoparticles with inherent biodegradability and no appreciable in vivo toxicity may be a unique type of multifunctional nanoplatform responsive to different parameters in the tumor microenvironment, promising for cancer theranostics with great efficacy. [ABSTRACT FROM AUTHOR]

By using different N-donor organic species as additional auxiliary ligands with structure-directing roles, four three-dimensional (3D) calcium-based coordination complexes, [Ca(dbt)(H2O)]n1, [Ca(H-dbt)2(5,5′-dmbpy)2]n2, (4,4′-bpy)0.5[Ca(dbt)(H2O)2]n3, and (H2-dib)[Ca3(dbt)4(H2O)4·2H2O]n4 (H2-dbt = 2,5-dibromoterephthalic acid, 2,2′-bpy = 2,2′-bipyridine, 5,5′-dmbpy = 5,5′-dimethyl-2,2′-bipyridine, 4,4′-bpy = 4,4′-bipyridine, dib = 1,4-di(1H-imidazol-1-yl)benzene), have been successfully synthesized under similar solvothermal conditions and structurally characterized. The organic amine molecules play different roles in the formation of four different metal–organic skeletons with diverse structural topologies, in which complexes 1–3 are neutral, and 4 comprises a negatively charged framework with diprotonated dib as the counterion. Complex 1 features a 3D (6,6)-connected framework structure composed of edge-sharing 1D Ca–O–Ca inorganic chains and dbt ligands. The 2,2′-bpy molecule plays an important role in the synthesis of 1 as the structure-directing agent (SDA). Complex 2 shows a 3D 2-fold interpenetrated diamondoid framework (dia, 66) formed by single metal nodes via linear H-dbt anions and bidentate chelating 5,5′-dmbpy ligands, while complex 3 exhibits a 3D noninterpenetrated pcu network with {412·63} topology constructed from binuclear [Ca2(CO2)4] secondary building units and two types of dbt ligands, in which 4,4′-bpy molecules are ordered within the 3D neutral calcium-based framework as template and space filling agents. Complex 4 is a unique (4,4,4,4,5)-connected 5-nodal topology net, in which the diprotonated dib molecules provide space filling to balance the negatively charged framework. In addition, the thermal stability and the fluorescence properties of complexes 1–4 have been investigated. [ABSTRACT FROM AUTHOR]

With the help of ascorbic acid as reductant, an exceedingly rare example of a visible single-crystal-to-single-crystal transformation from a CuII-framework to a CuI-chain under mild conditions has been observed, which involves the metal valence tautomerism and restructuring of bonds. The two compounds exhibit the properties of solvatochromism and luminescence aggregation-induced-emission towards CH3OH, respectively. [ABSTRACT FROM AUTHOR]

From 1-D to 3-D zinc coordination polymers based on multifunctional flexible 4-(1,2,4-triazole-methylene)-benzonitrile (tzbt), {[Zn(tzbt)2(bdc)]·2H2O}n(1), [Zn(tzbc)2]n(2), and [Zn(bpdc)(H2O)]n(3) (bdc = 1,4-benzenedicarboxylic acid, tzbc = 4-(1,2,4-triazole-methylene)-benzoic acid, bpdc = 4,4′-biphenyldicarboxylic acid), were synthesized under hydrothermal conditions. The tzbt was synthesized byN-alkylation and hydrolyzedin situto produce tzbc (in2). Single-crystal X-ray diffraction analysis reveals that1displays 1-D wave-like chains based on [Zn(bdc)]n.2is a chiral twofold interpenetrating 2-D architecture constructed with “V”-shaped tzbc.3is a 3-D chiral compound constructed from achiral H2bpdc with right-handed helical chains.1–3display stable blue-emitting luminescence with emission maxima ranging from 383 to 410 nm, depending on ligand-centeredπ*→πtransitions. The effects of different polarity solvents and temperature on luminescence are discussed. TGA and VT-XPRD reveal that2has thermal stability to 360 °C. [ABSTRACT FROM PUBLISHER]

Eight new metal–organic hybrid materials, namely {Cd(Tcph)(4,4′-bipy) 1/2 } ( 1 ), {[Cd 2 (Tcph) 2 (1,4-bimb) 1/2 (H 2 O) 4 ]·H 2 O} ( 2 ), {Cd 2 (Tcph) 2 (1,4-bmimb) 1/2 (H 2 O) 4 } ( 3 ), {Cd(Tcph)(1,2-bmimb)} ( 4 ), {Cu(Tcph)(1,4-bimb)(H 2 O)} ( 5 ), {[Co(Tcph)(1,4-bimb) 1/2 (H 2 O) 3 ]·(H 2 O)} ( 6 ), {Zn(Tcph)(1,2-bimb)} ( 7 ), {Cu 2 (Tcph) 2 (1,2-bimb)(H 2 O) 4 } ( 8 ), where Tcph=tetrachlorophthalate acid, 4,4′-bipy=4,4′-bipyridine, 1,4-bimb=1,4-bis(imidazol-1-ylmethyl)benzene, 1,4-bmimb=1,4-bis(2-methylimidazol-1-ylmethyl)benzene, 1,2-bimb=1,2-bis(imidazol-1-ylmethyl)-benzene, 1,2-bmimb=1,2-bis(2-methylimidazol-1-ylmethyl)benzene, have been synthesized and characterized. Their structures are determined by single crystal X-ray diffraction and further characterized by infrared spectra (IR) and thermogravimetric (TG) analyses. Complex 1 , 4 and 7 display 2D layer structures. 1 possesses two-dimensional sheet containing an unusual [Cd(Tcph)] chains linked by 4,4′-bipy co-ligand, while 4 and 7 hold the similar 4-connected 4 4 - sql nets. Complex 2 and 3 feature a similar three dimensional (3D) internal compensation structure with a topology of {4 2 ·6 3 ·8} 2 {6 3 }. 5 is a novel 2-fold self-penetrating 3D network with 4-coordinated 6 5 ·8–CdSO 4 subnets. The ladder-like chains of 6 are further connected through O–H···O interactions to yield a 3D supramolecular structure. 8 is a discrete tetranuclear complex. The thermal stabilities of 1–8 and the luminescent properties of 1–4 and 7 in the solid state are also discussed. [ABSTRACT FROM AUTHOR]

A new polyoxometalate based organic-inorganic hybrid [Ni 6 (trz) 2 (Htrz) 13 ][H 4 P 4 Mo 11 O 50 ]·7H 2 O was synthesized and exhibited high activity and selectivity for photoreduction of CO 2 under visible light. [Display omitted] • A new polyoxometalate named [Ni 6 (trz) 2 (Htrz) 13 ][H 4 P 4 Mo 11 O 50 ]·7H 2 O. • [Ni 6 (trz) 2 (Htrz) 13 ][H 4 P 4 Mo 11 O 50 ]·7H 2 O was synthesized under hydrothermal conditions. • [Ni 6 (trz) 2 (Htrz) 13 ][H 4 P 4 Mo 11 O 50 ]·7H 2 O form a binodal (4, 8)−connected gsp2 network. • [Ni 6 (trz) 2 (Htrz) 13 ][H 4 P 4 Mo 11 O 50 ]·7H 2 O has photocatalytic reduction of CO 2. A new polyoxometalate based organic-inorganic hybrid [Ni 6 (trz) 2 (Htrz) 13 ][H 4 P 4 Mo 11 O 50 ]·7H 2 O (1), constructed from a hexanuclear [Ni 6 (trz) 2 (Htrz) 13 ] building block and a new polyoxometalate [H 4 P 4 Mo 11 O 50 ] cluster, was synthesized under a hydrothermal condition. In this 3D structure, each [Ni 6 (trz) 2 (Htrz) 13 ] secondary building unit (SBU) connects with four neighbored [Ni 6 (trz) 2 (Htrz) 13 ] and four [H 4 P 4 Mo 11 O 50 ] clusters, forming an eight-connected node. While each [H 4 P 4 Mo 11 O 50 ] cluster bridges four [Ni 6 (trz) 2 (Htrz) 13 ] SBUs as a four-connected node. So the 3D framework of 1 can be simplified to a binodal (4, 8)–connected gsp2 topology with point symbol [44·62][416·612]. The photocatalytic reduction of CO 2 under visible light reveals that the highest yield of CO was 689.86 μmol g−1 when 1 is used as catalyst, Ru(bpy) 3 Cl 2 as a photosensitizer and TEOA as a sacrificial agent. The mechanism of the photoreduction of CO 2 is confirmed by Mott-Schottky, photocurrent, and fluorescence quenching experiments. This research provides a new strategy for the design of cheap and efficient POM-based photocatalysts. [ABSTRACT FROM AUTHOR]