Coordination Site Selective Occupation Strategy for Tuning the Photosalient Effects of Photoactive Cd Complexes.

The application of photo responsive crystals to useful actuation demands a rational design to elicit controllable movement. The [2+2] photocycloaddition reaction triggers mechanical motion  using associated photosalient (PS) effects. We herein report a coordination site selective occupation strategy to modulate the arrangement of C=C bonds and thereby tune the PS effect. Replacing or repositioning the donor atom at one end of the linear ligand allowed for a greater level of molecular structural flexibility, facilitating [2+2] photocycloaddition. The distance between photoreactive centres and coordination sites was adjusted by ligand design to regulate PS behavior. This work suggests new avenues for modulating PS movement to achieve useful motion.

A Phosphorescent P/N/S Hybrid Ligand Stabilized Au2Cu Complex Selectively Senses Ammonia and Amines.

Reaction of a P/N/S hybrid ligand dpppyatc (N,N-bis((diphenylphosphaneyl)methyl)-N-(pyridin-2-yl)-amino-thiocarbamide) with Au(tht)Cl (tht=tetrahydrothiophene) and [Cu(MeCN)4]BF4 afforded cluster complex [Au2Cu(dpppyatc)2](BF4)2Cl (1). Upon excitation at 480 nm, 1 emitted orange phosphorescence at 646 nm, which was red-shifted to ~698 nm selectively in the presence of ammonia or amine vapor. This chromic photoluminescent response toward ammonia was sensitive and reversible. Complex1 could detect ammonia in aqueous solution down to concentrations of 2 ppm (w/w).

A Multiple Stimuli-Responsive Ag/P/S Complex Showing Solvochromic and Mechanochromic Photoluminescence.

The reaction of CF3COOAg, 3-bdppmapy (N,N-bis(diphenylphosphanylmethyl)-3-aminopyridine) and HTZ (1,2,4-triazole-3-thiol) in CH2Cl2/MeOH resulted in a dinuclear Ag/P/S complex [Ag2(TZ)2(3-bdppmapy)2]·xSol (1·xSol). Crystals of 1·xSol converted to 1·2MeOH in air at room temperature and further to 1 under vacuum upon heating. The solid-state, room-temperature photoluminescent emission of 1·xSol (510 nm) shifted to 494 nm (1·2MeOH) and 486 nm (1). Grinding solids of 1·2MeOH in air resulted in amorphous 1G characterized by solid-state emission at 468 nm, which converted to 1GR with 513 nm emission upon MeOH treatment. Grinding 1GR in air returned 1G, and this interconversion was reproducible over five cycles. The solid-state photoluminescence of 1G changed in response to vapors containing low-molecular weight alcohols but remained unchanged after exposure to other volatile organic compounds (VOCs) or to water vapor. Test papers impregnated with 1G could detect methanol in vapors from aqueous solutions at concentrations above 50%. Complex 1G is, therefore, an example of a stimuli-responsive molecular sensor for the detection of alcohols.

Heteroleptic copper(I) complexes [Cu(dmp)(N

Earth-abundant copper(I) coordination complexes of an imine-phosphine and a diimine have been developed as visible-light photocatalysts. Reaction of [Cu(MeCN)4]BF4 with hetero-bidentate phosphinopyrazole (phpz) ligand R1R2C3HN2PPh3 (R1 = R2 = H (1a); R1 = H, R2 = Me (1b); R1 = H, R2 = Ph (1c); R1 = R2 = Me (1d)) and 2,9-dimethyl-1,10-phenanthroline (dmp) gave four heteroleptic bis-chelate Cu(I) complexes [Cu(dmp)(R1R2C3HN2PPh3)]BF4 (R1 = R2 = H (2a); R1 = H, R2 = Me (2b); R1 = H, R2 = Ph (2c); R1 = R2 = Me (2d)) with distorted tetrahedral geometries. Complexes 2a-2d exhibited broad absorption in the visible spectrum and could facilitate photochemical intermolecular atom-transfer radical addition reactions of CBr4, or CCl3Br, CHI3 to styrenes in yields up to 91% and with a broad substrate scope. The absorption, emission, redox potential and photocatalytic activity were dependent on the substituents on the phpz ligand. Mechanistic studies supported an atom-transfer radical addition (ATRA) mechanism.

One-Dimensional Heterobimetallic Au/Ag Coordination Polymer Showing a Selective, Reversible, and Visible Vapor-Chromic Photoluminescent Response toward Methanol.

A heterobimetallic coordination polymer [Au4(dppmt)4(AgCl)2]n (1) incorporating an in situ generated P-S ligand (dppmtH) was synthesized from the solvothermal reaction of Au(tht)Cl, AgCl, and dpppyatc in CH3CN/CH2Cl2 (dppmtH = (diphenylphosphino)methanethiol, tht = tetrahydrothiophene, dpppyatc = N,N-bis((diphenylphosphaneyl)methyl)-N-(pyridin-2-yl)-amino-thiocarbamide). The structure of 1 contains a one-dimensional helical Au-Au chain in which the unique [Au4Ag2S2] cluster units are connected by [Au2(dppmt)2] dimers. Upon excitation at 343 nm, 1 exhibited cyan (495 nm) phosphorescent emission at quantum yield (QY) = 22.3% and τ = 0.78 µs (λex = 375 nm). Coordination polymer 1 exhibited a rapid, selective, reversible, and visible vapor-chromic response on exposure to methanol (MeOH) vapor with its emission shifting to a more intense green (530 nm, λex = 388 nm) with QY = 46.8% and τ = 1.24 µs (λex = 375 nm). A polymethylmethacrylate film containing 1 served as a reversible chemical sensor for the sensitive detection of MeOH in air.

Silver(I) Coordination Polymer Ligated by Bipyrazole Me4bpzH2, [Ag(X)(Me4bpzH2)] (X = CF3CO2- and CF3SO3-, Me4bpzH2 = 3,3',5,5'-Tetramethyl-4,4'-bipyrazole): Anion Dependent Structures and Photoluminescence Properties.

Coordination polymers of transition metal ions are fascinating and important to coordination chemistry. One of the ligands known to form particularly interesting coordination polymers is 3,3',5,5'-tetramethyl-4,4'-bipyrazole (Me4bpzH2). Group 11 metal(I) ion coordination polymers, other than those of copper(I), are relatively easy to handle because of their low reactivity towards dioxygen and moisture. However, the known silver(I) coordination polymers often have poor solubility in common solvents and so cannot be easily analyzed in solution. By using a tetramethyl substituted bipyrazole ligand, we have synthesized more soluble silver(I) complexes that contain the trifluoromethyl group in the coordinated ions CF3CO2- and CF3SO3- in [Ag(CF3CO2)(Me4bpzH2)] and [Ag(CF3SO3)(Me4bpzH2)]. We determined both structures by single-crystal X-ray analysis at low temperatures and compared them in detail. Moreover, we investigated the solution behavior of these coordination polymers by 1H-NMR, IR, Raman, UV-Vis spectroscopies, and their low-temperature, solid-state photoluminescence. The high-energy band at ~330 nm corresponded to ligand-centered (bipyrazole) fluorescence, and the low-energy band at ~400 nm to ligand-centered phosphorescence resulting from the heavy atom effect.

Nanoscale Two-Dimensional FeII- and CoII-Based Metal-Organic Frameworks of Porphyrin Ligand for the Photodynamic Therapy of Breast Cancer.

The delivery of biocompatible reagents into cancer cells can elicit an anticancer effect by taking advantage of the unique characteristics of the tumor microenvironment (TME). In this work, we report that nanoscale two-dimensional FeII- and CoII-based metal-organic frameworks (NMOFs) of porphyrin ligand meso-tetrakis (6-(hydroxymethyl) pyridin-3-yl) porphyrin (THPP) can catalyze the generation of hydroxyl radicals (•OH) and O2 in the presence of H2O2 that is overexpressed in the TME. Photodynamic therapy consumes the generated O2 to produce a singlet oxygen (1O2). Both •OH and 1O2 are reactive oxygen species (ROS) that inhibit cancer cell proliferation. The FeII- and CoII-based NMOFs were non-toxic in the dark but cytotoxic when irradiated with 660 nm light. This preliminary work points to the potential of porphyrin-based ligands of transition metals as anticancer drugs by synergizing different therapeutic modalities.

A Novel Photoluminescent Ag/Cu Cluster Exhibits a Chromic Photoluminescence Response towards Volatile Organic Vapors.

A new Ag/Cu bimetallic cluster [Ag10Cu6(bdppthi)2(C≡CPh)12(EtOH)2](ClO4)4 (1, bdppthi = N,N'-bis(diphenylphosphanylmethyl)-tetrahydroimidazole) exhibited strong phosphorescent (PL) emission at 644 nm upon excitation at 400 nm. Removal of the coordinated EtOH molecules in 1 resulted in derivative 1a, which exhibited significant red-shifted emission at 678 nm. The structure and PL of 1 was restored on exposure to EtOH vapor. Cluster 1a also exhibited a vapor-chromic PL response towards other common organic solvent vapors including acetone, MeOH and MeCN. A PMMA film of 1a was developed as a reusable visible sensor for MeCN.

Coordination Polymer-Mediated Molecular Surgery for Precise Interconversion of Dicyclobutane Compounds.

A Cd(II)-based coordination polymer {[Cd2(5-F-1,3-bpeb)2(FBA)4]·H2O}n (CP1) was obtained from Cd(II) salt, 5-fluoro-1,3-bis[2-(4-pyridyl)ethenyl]benzene (5-F-1,3-bpeb), and p-fluorobenzoic acid (HFBA). Within the one-dimensional chain structure of CP1, a pair of 5-F-1,3-bpeb was arranged in a face-to-face style. Upon UV irradiation and heat treatment, multiple cyclobutane isomers, including specific monocyclobutanes (1 with an endo-cyclobutane ring in CP1-1 and 1' with an exo-cyclobutane ring in CP1-1') and dicyclobutanes (endo,endo-dicyclobutane 2α in CP1-2α, exo,endo-dicyclobutane 2ß in CP1-2ß, and exo,exo-dicyclobutane 2γ in CP1-2γ) were stereoselectively produced. These isomers could be interconverted inside the CP via cutting/coupling specific bonds, which may be regarded as a type of molecular surgery. The precision of cutting/coupling relied on the thermal stability of the cyclobutanes and the alignment of the reactive alkene centers. The conversion processes were tracked through nuclear magnetic resonance, in situ powder X-ray diffraction, and IR spectroscopy. This approach can be considered as skeletal editing to construct complex organic compounds directly from one precursor.

Ni(II)-Mediated Photochemical Oxidative Esterification of Aldehydes with Phenols.

The photopromoted, Ni-catalyzed acceptorless dehydrogenation esterification of phenols and aromatic aldehydes has been achieved in an oxidant- and external photosensitizer-free manner. This reliable and atom-economical transformation was tolerant to a wide range of functional groups and proceeded efficiently to give various aryl benzoates in moderate to high yields. Additionally, this photocatalytic system displayed high activity for the hydrogen-evolution cross coupling of aliphatic aldehydes and phenols employing dual nickel and aromatic aldehyde catalysis.

Novel Catabolic Pathway of Quercetin-3-O-Rutinose-7-O-α-L-Rhamnoside by Lactobacillus plantarum GDMCC 1.140: The Direct Fission of C-Ring.

Lychee pulp phenolics (LPP) is mainly catabolized in the host colon, increasing the abundances of Bacteroides and Lactobacillus. Herein, five selected gut microbial strains (Bacteroides uniformis, B. thetaiotaomicron, Lactobacillus rhamnosus, L. plantarum, and L. acidophilus) were separately incubated with LPP to ascertain the specific strains participating in phenolic metabolism and the corresponding metabolites. The results indicated that B. uniformis, L. rhamnosus, and L. plantarum were involved in LPP utilization, contributing to 52.37, 28.33, and 45.11% of LPP degradation after 48 h fermentation, respectively. Unprecedentedly, the metabolic pathway of the major phenolic compound quercetin-3-O-rutinose-7-O-α-L-rhamnoside by L. plantarum, appeared to be the direct fission of C-ring at C2-O1 and C3-C4 bonds, which was proved from the occurrence of two substances with the deprotonated molecule [M-H]- ion at m/z 299 and 459, respectively. Meanwhile, it was fully confirmed that B. uniformis participated in the catabolism of isorhamnetin glycoside and procyanidin B2. In the B. uniformis culture, kaempferol was synthesized through dehydroxylation of quercetin which could be catabolized into alphitonin by L. rhamnosus. Furthermore, LPP metabolites exerted higher antioxidant activity than their precursors and gave clues to understand the interindividual differences for phenolic metabolism by gut microbiota.

Visible-light-driven C(sp2)-H arylation of phenols with arylbromides enabled by electron donor-acceptor excitation.

We have developed a catalyst-free visible-light-driven C(sp2)-H arylation of unprotected phenols with arylbromides to give 2-arylated phenols. This reaction proceeds through the excitation of an electron donor-acceptor complex between a phenolate and an arylbromide, electron transfer, and debrominative C(sp2)-C(sp2) coupling.

Improved Efficiency and Stability of Red Phosphorescent Organic Light-Emitting Diodes via Selective Deuteration.

The secondary kinetic isotope effects (KIEs) of red phosphorescent Ir(III) complexes and the corresponding devices have been investigated. The selective deuterated red emitters show negligible influence on the luminescent spectra, but have positive effects on the quantum efficiencies and stabilities in the devices. As secondary KIEs predicted, the photolysis coinciding with the electrolysis of the deuterated complexes in the devices, measured via decreasing of luminescent intensity, are reduced in rate. An about 33% increase of the device working lifetime could be readily obtained with the strategy of selective deuteration on the emitter complexes. The findings demonstrate the importance of the isotopic effect on the performance improvement of organic light emitting devices and will also trigger the study on organic optoelectronic materials via isotopic tools.

Tunable photosalient behaviours within coordination polymers via functional molecular prearrangements.

Four Cd(II)/diene coordination polymers (CPs) with similar 1D chain motifs exhibit different photosalient (PS) behaviours in response to UV light. The [2+2] photoreaction between the CC groups within these CPs results in diverse PS behaviours of their crystals with different CC pair arrangements. The interesting PS behaviours of these CPs can be applied in design and fabrication of advanced photoactuating materials.

New structurally diverse photoactive cadmium coordination polymers.

Four structurally diverse coordination polymers 1-4 (CP1-CP4) were designed and constructed from Cd(II) ions and various carboxyl ligands (H2oba, 4,4'-oxydibenzoic acid; H2bpa, (E)-4,4'-(ethene-1,2-diyl)dibenzoic acid; H2pbda, 4,4'-((1,3-phenylenebis(methylene))bis(oxy))dibenzoic acid) and the alkene containing ligand (CH3-bpeb, 4,4'-((1E,1'E)-(2,5-dimethyl-1,4-phenylene)bis(ethene-2,1-diyl))dipyridine). CP1-CP4 possess Cd2 binuclear secondary building units (SBUs). The geometry of the dicarboxylate ligands and the reaction conditions determined the final structure with a variety of motifs. CP1 possesses an interdigitated 2D structure, while CP2 consists of a 1D channel-like motif with isolated CH3-bpeb molecules embedded in the channels. The solid-state structure of CP3 consists of two unique layers interpenetrated to form a 2D + 2D → 2D polycatenated backbone, while a 1D channel-like motif filled by isolated CH3-bpeb molecules was observed for CP4. In all four coordination polymers pairs of CH3-bpeb molecules were bound or encapsulated by the Cd2 secondary building units at an appropriate distance and orientation for solid-state [2 + 2] photodimerization of one pair of CC bonds. Desolvation of CP3 with heat resulted in a decrease in solid-state fluorescence and a slowing of the rate of solid-state photodimerization.

A photoluminescent thermometer made from a thermoresponsive tetranuclear gold complex and phosphor N630.

Reaction of [(3-bdppmapy)(AuCl)2] with NaHmba (3-bdppmapy = N,N'-bis-(diphenylphosphanylmethyl-3-aminopytidine, H2mba = 2-mercaptobenzoic acid) resulted in a new tetranuclear Au/P/S complex [(3-bdppmapy)2(AuHmba)3(AuCl)] (1). Upon excitation at 370 nm, 1 exhibited solid state, room temperature, green fluorescent emission (QY = 4.7%, τ = 2.58 ns) which was significantly enanced at lower temperatures due to strengthening of the Au-Au interaction. Different ratios of 1 with phosphor N630 in PMMA were used to make thermochromic photoluminescent films and fibres that could be fabricated into an optical thermometer sensitive over temperature ranges 80-300 K and 300-370 K.

The Influence of Aryl Substituents on the Supramolecular Structures and Photoluminescence of Cyclic Trinuclear Pyrazolato Copper(I) Complexes.

Cyclic trinuclear complexes with group 11 metal(I) ions are fascinating and important to coordination chemistry. One of the ligands known to form these cyclic trinuclear complexes is pyrazolate, which is a bridging ligand that coordinates many transition metal ions in a Npz-M-Npz linear mode (Npz = pyrazolyl nitrogen atom). In these group 11 metal(I) ions, copper is the most abundant metal. Therefore, polynuclear copper(I) complexes are very important in this field. The cyclic trinuclear copper(I) complex [Cu(3,5-Ph2pz)]3 (3,5-Ph2pz- = 3,5-diphenyl-1-pyrazolate anion) was reported in 1988 as a landmark complex, but its photoluminescence properties have hitherto not been described. In this study, we report the photoluminescence and two different polymorphs of [Cu(3,5-Ph2pz)]3 and its derivative [Cu(3-Me-5-Phpz)]3 (3-Me-5-Phpz- = 3-metyl-5-phenyl-1-pyrazale anion). The substituents in [Cu(3-Me-5-Phpz)]3 cause smaller distortions in the solid-state structure and a red-shift in photoluminescence due to the presence of intermolecular cuprophilic interactions.

Low-Threshold Amplified Spontaneous Emission from Air-Stable CsPbBr3 Perovskite Films Containing Trace Amounts of Polyethylene Oxide.

Organic additives can enhance the amplified spontaneous emission (ASE) performance of inorganic cesium lead halide perovskites (CsPbBr3 ) but volatility, potential hygroscopicity and oxidative degradation of these additives jeopardizes the thermal stability and shelf-life of blended CsPbBr3 films. To address this problem, we have fabricated perovskite films in a two-step solution protocol involving as little added polyethylene oxide (PEO) as possible. These films exhibited enhanced crystallization, improved photoluminescence (PL) intensity and prolonged lifetimes. Their hierarchical morphology and surface passivation lowered the ASE threshold from 278 to 176 µÐˆ/cm2 under one-photon nanosecond laser excitation. The proportion of added PEO was 0.3 wt% and was subsequently almost fully removed, thereby reducing its adverse influence on the stability of resulting films under continuous pulsed laser excitation. Stable ASE spectra could be stimulated after storage in air for 10 months.

Real-Time Monitoring of Surface Effects on the Oxygen Reduction Reaction Mechanism for Aprotic Na-O2 Batteries.

Discharging of aprotic sodium-oxygen (Na-O2) batteries is driven by the cathodic oxygen reduction reaction in the presence of sodium cations (Na+-ORR). However, the mechanism of aprotic Na+-ORR remains ambiguous and is system dependent. In-situ electrochemical Raman spectroscopy has been employed to study the aprotic Na+-ORR processes at three atomically ordered Au(hkl) single-crystal surfaces for the first time, and the structure-intermediates/mechanism relationship has been identified at a molecular level. Direct spectroscopic evidence of superoxide on Au(110) and peroxide on Au(100) and Au(111) as intermediates/products has been obtained. Combining these experimental results with theoretical simulation has revealed that the surface effect of Au(hkl) electrodes on aprotic Na+-ORR activity is mainly caused by the different adsorption of Na+ and O2. This work enhances our understanding of aprotic Na+-ORR on Au(hkl) surfaces and provides further guidance for the design of improved Na-O2 batteries.

Structural modulation induced by cobalt-based ionic liquids for enhanced thermoelectric transport in PEDOT:PSS.

Poly(3,4ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) has been intensively studied for its thermoelectric applications. Structural modulation to improve crystalline ordering, chain conformation and film morphology is a promising way to decouple the trade-off between conductivity and Seebeck coefficient and thus improve the thermoelectric power factor. Post treatment with ionic liquid ([CoCl2 ⋅ 6H2 O]:[ChCl]) bearing cobalt-containing anions resulted in a remarkable enhancement of the power factor to 76.8 µW m-1 K-2 . This IL combines the influence of a high-boiling polar organic solvent and diffusing ions. A high σ mainly resulted from the efficient removal of PSS chains, ordering of the structure and delocalization of bipoloran-dominant transport after conformational change. The increase in S was not due to dedoping of PEDOT chains, but rather the sharp feature of the density of states at the Fermi level induced by ion-exchange with unconventional anions.