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A zwitterionic ligand 3-(triethylammonio)propyne (TAP) has been employed to construct nine silver ethynide compounds for the first time. Single-crystal X-ray analyses reveal that compounds 1 and 2 are silver ethynide assemblies based on the Ag3 subunits and clusters 3-8 are small discrete clusters of Ag3, Ag6, Ag8, and Ag12, respectively, ligated by the bulky TAP ligand with different auxiliary ligands. In addition, upon acquiring the tripod-like tBuPO32-, a unprecedented 80 nuclei silver ethynide cluster was isolated and determined to be [(CF3CO2)5@Ag80(TAP)14(tBuPO3)16(CF3CO2)24]19+ by crystallography and thermogravimetric analysis. The C1 symmetry of Ag80 was deconstructed to be two [Ag40(TAP)7(tBuPO3)8(CF3CO2)12]12+ secondary building subunits arranged in a cross way, with five CF3CO2- trapped in the center. These results highlight that the elaborate selection of ethynide ligands is of great importance in the synthesis of novel silver ethynide clusters.

Herein, in this study, we utilized Ag+-ligand interactions for critically regulating the morphology of carbon by the Stober-silica/carbon co-assembly method for the first time. Tetraethyl orthosilicate (TEOS) and resorcinol/formaldehyde (RF) assemble upon dictation by Ag+ and pyridyl-functionalized surfactants, producing porous carbon tubes (RF1) with a high surface area of 696 m2 g-1 and accessible mesopores ∼15 nm in size. Furthermore, when using tetrapropyl orthosilicate (TPOS) with a slower hydrolysis rate than that of TEOS, carbon tubes (RF2) with enhanced uniformity and a surface area as high as 2112 m2 g-1 are generated. Additionally, when using dopamine hydrochloride instead of RF as a carbon precursor, tubular polydopamine (TDA) with lengths of tens of microns is fabricated, which exhibits excellent catalytic activity toward oxygen reduction reactions in alkaline solutions due to its unique structural feature, a high surface area of 1350 m2 g-1, metallic silver remains of 8.3 wt%, and a rich nitrogen content of 3.6 wt%. This work sheds light on the engineering of a micellar soft template and synthesizing novel nanostructures by the extension of the Stober method.

Four silver thiolate clusters, [H3 O][(Ag3 S3 )(BF4 )@Ag27 (tBuS)18 (hfac)6 H2 O]⋅H2 O (1; hfac = hexafluoroacetylacetone), [(Ag3 S3 )(CF3 CO2 )@Ag30 (tBuS)16 (CF3 CO2 )9 (CH3 CN)4 ]⋅CF3 CO2 ⋅4 CH3 CN (2), [(Ag3 S3 )(MoO4 )@Ag30 (tBuS)16 (CF3 CO2 )9 (CH3 CN)4 ]⋅2 CH3 CN (3), and [(Ag3 S3 )(CrO4 )@Ag30 (tBuS)16 (CF3 CO2 )9 (CH3 CN)4 ]⋅4 CH3 CN (4), were isolated. They have similar nestlike structures assembled by an [Ag3 S3 ]3- template together with one of the BF4 - , CF3 CO2 - , MoO4 2- , or CrO4 2- anions. Interestingly, the solid-state emissions of 2-4 are dependent on the templating anions and are tunable from green to orange and then to red by changing the template from CF3 CO2 - to MoO4 2- and to CrO4 2- , and this may be correlated to the charge transfer between these templates to metal atoms. This work helps to understand the templating role of heteroanions and the relationship between structure and properties.

Constructing silver(i)-thiolate clusters from simple building blocks usually involves elusive self-assembly processes and remains a long-standing challenge. In this work, we report 6 silver(i)-thiolate clusters protected by pyridines, namely, [Ag3(tBuS)2(Py)(NO3)]n (Py = pyridine) (1), [Ag10(tBuS)6(Py)6(CF3CO2)4]·3Py (2), [Ag12(iPrS)6(Py)8(NO3)6]·2H2O (3), Ag12(iPrS)6(Py)8(CF3CO2)6 (4), Ag12(iPrS)6(4-ap)6(NO3)6 (4-ap = 4-aminopyridine) (5), and [Ag50S13(tBuS)20(Py)12]·4BF4·4Py·4CH3OH·2H2O (6). Single-crystal X-ray crystallography analysis reveals that six clusters are constructed by four types of structural blocks, including the PyAg(tBuS)2 monomer, Py2Ag2(tBuS)2 dimer, Py3Ag3(tBuS)3 trimer and (4-ap)6Ag6(iPrS)6 hexamer. Notably, cluster 6 consists of a rhombic dodecahedron S@Ag14 kernel with 12 interstitial S2- atoms encapsulated by 8 μ4-tBuS- ligands, as well as six unique butterfly-like (Py)2Ag6(tBuS)2 staple motifs composed of a Py2Ag2(tBuS)2 dimer and four silver ions. Moreover, it is found that pyridine ligands have important influence on the construction of silver thiolate clusters and their Ag-SR bond lengths.

Atomically precise silver clusters with tunable photoluminescence (PL) properties have attracted extensive attention due to their great value for basic science and future applications. Here, we report that the addition of a sulfido template into a triangular thiolated silver cluster [Ag11(iPrS)9(dppb)3]·2CF3SO3·CH3OH (Ag11, dppb = 1,4-bis(diphenylphosphino)butane), which is emissive at 660 nm under ambient conditions, produced another silver cluster [S@Ag15(sBuS)12(dppb)3]·CF3SO3·H2O (Ag15) that displays 716 nm emission with a 56 nm redshift aided by the ligand sec-butyl mercaptan. The sulfido template, which affects the geometrical and electronic structures, results in a redshift of Ag11 room-temperature PL as a result of opening up the template-to-metal charge transfer (TMCT) and disturbing the electronic transition between the metal core and ligands at the periphery.

Herein, in this study, we utilized Ag+-ligand interactions for critically regulating the morphology of carbon by the Stöber-silica/carbon co-assembly method for the first time. Tetraethyl orthosilicate (TEOS) and resorcinol/formaldehyde (RF) assemble upon dictation by Ag+ and pyridyl-functionalized surfactants, producing porous carbon tubes (RF1) with a high surface area of 696 m2 g-1 and accessible mesopores ∼15 nm in size. Furthermore, when using tetrapropyl orthosilicate (TPOS) with a slower hydrolysis rate than that of TEOS, carbon tubes (RF2) with enhanced uniformity and a surface area as high as 2112 m2 g-1 are generated. Additionally, when using dopamine hydrochloride instead of RF as a carbon precursor, tubular polydopamine (TDA) with lengths of tens of microns is fabricated, which exhibits excellent catalytic activity toward oxygen reduction reactions in alkaline solutions due to its unique structural feature, a high surface area of 1350 m2 g-1, metallic silver remains of 8.3 wt%, and a rich nitrogen content of 3.6 wt%. This work sheds light on the engineering of a micellar soft template and synthesizing novel nanostructures by the extension of the Stöber method.

It has been reported that 3, 5-bis(3,6-di-tert-butyl-9H-carbazol-9-yl)-phenyl)(pyridin-4-yl)meth (DTCBPy) is an efficient thermally activated delayed fluorescence (TADF) molecule. We designed a series of the isomeric molecules (2–5) of DTCBPy (1) by changing the position of nitrogen atom in the acceptor and the substituent position of donor units. The highest occupied molecular orbitals (HOMO) of 1–5 are all delocalized over the donor units, and the lowest unoccupied molecular orbitals (LUMO) are located on the acceptor unit. As expected from frontier molecular orbital analysis, the singlet-triplet energy splitting (ΔEST) values of 1–5 are in a small range from 0.087 to 0.147 eV, indicating the easy realization of reverse intersystem crossing from the lowest triplet to singlet excited states. However, the structural modification has a significant influence on the fluorescence radiative rate (kr), which varies from 3.49× 106 to 2.04 × 107 s−1 for 1–5. This work is expected to provide valuable information for synthesizing highly efficient TADF materials based on DTCBPy.

tert-Butylphosphonic acid and rare-earth precursors are employed to construct four trinuclear rare-earth phosphonate clusters, RE3(tBuPO3)2(hfac)5(CH3OH)8]·2CH3OH (RE = Eu, Y, Pr, and Sm; hfac = hexafluoroacetylacetonate), which are composed of three RE3+ ions alternately bridged by two phosphonates. With the introduction of bismuth oxido diketonate, [Bi9O7(hfac)13], three different types of rare-earth/bismuth phosphonate clusters, Bi12RE2 (RE = Pr and Sm), Bi6Eu7, and Bi6Y9, are successfully obtained via variation of the reaction conditions, and they are the first reported examples of bismuth–oxo clusters encapsulated by cyclic rare-earth–oxo or rare-earth/bismuth–oxo phosphonate clusters, respectively. These clusters show obvious absorption in the UV region, and the Eu-containing clusters exhibit bright-red fluorescence.

Reaction of AgC≡CtBu with (EtO)2PS2Na at room temperature leads to the isolation of two new silver(I)-ethynide compounds incorporating the dithiophosphate ligand, namely, {CO3@(Ag3)4(C≡CtBu)4(EtO)2PS2]6}·0.5H2O (1) and {(CO3)2@Ag26(C≡CtBu)16[(EtO)2PS2]4}·2(OH)·4MeOH·6H2O (2). Besides, we obtain another three silver(I)-ethynide clusters S@Ag11(C≡CtBu)2[(EtO)2PS2]7 (3), {S@Ag14(C≡CPh)8[(EtO)2PS2]4(TMEDA)2}·5MeOH (4), and {S@Ag14(C≡CPh)8[(iPrO)2PS2]4(TMEDA)2}·7CH3OH (5), with AgC≡CR (R= tBu, Ph) and (RO)2PS2Na (R= Et, iPr) as the starting materials. Complexes 1–2 are templated by a carbonate anion in situ generated from the fixation of atmospheric CO2 in a basic TMEDA-containing solution, and TMEDA can also lead to the disassembly of dithiophosphate to give a sulfide ion as the template for the generation of 3–5.

tert-Butylphosphonic acid and lanthanide precursors were employed to construct two high-nuclearity hybrid silver(I)-ytterbium(III) phosphonate clusters: compound 1 consists of a Ag16 ethynide cluster fused with a trinuclear hydroxoytterbium phosphonate cluster, whereas compound 2 is composed of two Ag16 ethynide clusters bridged by a hexanuclear oxo/hydroxoytterbium phosphonate cluster. Using transition-metal-substituted lacunary polyoxotungstates in place of the lanthanide reactant, new phosphonate-functionalized silver(I)-copper(II) ethynide clusters [Ag34 Cu6 (3) and Ag37 Cu6 (4)] and silver(I) ethynide clusters [Ag51 (5) and Ag72 (6)] were obtained. The structures of complexes 3-6 feature core-shell arrangements, in which silver(I)-copper(II) or silver(I) ethynide cluster shells stabilized by peripheral phosphonate ligands enclose different kinds of tungstate core templates.

Phosphonate ligands as structure-directing components have been employed to construct four new high-nuclearity silver(I) sulfide-ethynide-thiolate clusters, in which silver(I) aggregates tBuC≡C⊃Ag3, tBuC≡C⊃Ag4, and 2tBuC≡C⊃Ag7 are bridged by tBuS– ligands to engender respective silver(I) ethynide-thiolate clusters functioning as integral shell components, which are supported by phosphonate ligands. In each silver(I) sulfide-ethynide-thiolate cluster, a different encapsulated silver sulfide cluster serves as a core template.

The case that aggregation brings a huge influence on the structure and fluorescent property of 5-(4-(1,2,2-triphenylvinyl)phenyl)thiophene-2-carbaldehyde (P4TA) was detailedly investigated here by employing both quantum mechanics and molecular mechanics. Besides the isolated molecule, the aggregated molecule both in water and crystal state was studied by focusing on the comparison of photoelectronic properties, including the geometrical and electronic structures at ground and excited states, emission and internal conversation properties. For the aggregation state, the intermolecular interaction was employed to explain the difference in structure, emission color and intensity of different polymorphs. The noticeable contribution from low-frequency region, corresponding to the four phenyl rings twisting vibration, to the Huang-Rhys factor and reorganization energy, as well as the possible potential energy surface crossing between S0 and S1 states for isolated molecules was considered as the reason of its aggregation induced emission (AIE) performance. Importantly, the aggregation process in water simulated at the same time helps us to have a deeper understanding of the AIE behavior of P4TA, which also provides another perspective to explore the AIE phenomenon in theory.

The high-nuclearity silver(I) clusters, a novel class of supramolecular assembly of silver(I) complexes, were usually prepared by incorporating silver ions with various ligands. Notably, a large number of argentophilic interactions exist in the high-nuclearity silver clusters. These interactions influence significantly a variety of structural and other physical characteristics. Thus, we will summarize the synthesis and structure of high-nuclearity silver(I) clusters with chalcogenide [E] 2− (E = S, Se and Te), chalcogenolate [RE] − (E = S, Se and Te), dichalcogenophosphate [(RO) 2 PE 2 ] − (E = S and Se), and dichalcogenophosphonate [R(R’O)PS 2 ] − or [RP(O)S 2 ] 2− . This results in deeper understanding of the relationship between synthesis conditions and the finally isolated products. The literature survey is up to December 2015 and the review represents the first article covering the span of various types of high-nuclearity Ag-E clusters and should contribute considerable value for future research.

Polynucleating oxygen donor ligands as precursors have been employed to construct three high-nuclearity heterometallic ethynide clusters. Compound 2 consists of a Cl@Ag12 ethynide cluster capped by two trinuclear organooxotin phosphonate clusters [(nBuSn)3(μ3-O)(tBuPO3)3(OMe)(OH)2]2-. Compound 3 consists of a Ag8 ethynide cluster fused with a nonanuclear oxo-bismuth phosphonate cluster [Bi9O6(tBuPO3)9(tBuPO3H)]4-, while compound 4 is composed of two Cl@Ag15 ethynide clusters bridged by a hexanuclear oxo/hydroxo-bismuth phosphonate cluster [Bi6O4(OH)4(tBuPO3)6(hfac)2(CF3COO)2]10-.

The n-butylphosphonate ligand has been employed to construct three new silver(I) thiolate compounds. Single-crystal X-ray analysis revealed that complexes 1 and 2 are Ag48 and Ag51 coordination chain polymers, while 3 contains a discrete Ag48 cluster, in which three different kinds of silver(I) thiolate cluster shells enclose three different phosphonate-functionalized silver(I) cluster cores, respectively. The structures of clusters in 1-3 feature three three-shell arrangements, S@Ag12 @(nBuPO3 )9 @Ag36 S23 , S@Ag11 @(nBuPO3 )7 (MoO4 )2 @Ag40 S27 and MoO4 @Ag12 @(nBuPO3 )8 S6 @Ag36 S24 , respectively.

A water-soluble fluorescent probe was described for detecting hydrogen peroxide with the naphthalimide derived as fluorophore and boronate moiety as recognition unit. The probe was developed as a turn-on fluorescent chemosensor with fast, high selectivity and sensitivity toward H2O2over other biological reactive oxygen species. What is more, the probe was linear response to H2O2concentration in the range of 2.5×10−8– 3.2×10−5M and lower detection limit down to 12 nM (S / N = 3) was obtained.

The geometries, electronic structures, absorption spectra and the character of excited state for the reported p-type sensitizers O2, O6 and O7 and designed 1–5 with different π-linkers were investigated by DFT and TDDFT calculations, to reveal the influences of π-linkers on the performance of DSSCs. It is found that the higher IPCE of O7 as compared to O6 stems from the improved light harvesting efficiency (LHE) and the efficient regeneration. And, for O2 and O6 with comparable IPCE, the slightly increased Jsc for O2 can be mainly ascribed to the better spectrum matching with solar spectrum. The results also revealed that the calculated charge transfer index (DCT, the metric of photoinduced electron–hole separation) for reported sensitizers is well correlated with the measured electron lifetime pertaining to Voc. Importantly, dye 4 may be a promising candidate for the p-type sensitizer due to the red-shifted absorption, larger LHE and longer DCT in comparison with prototype O7.

A water-soluble fluorescent probe was described for detecting hydrogen peroxide with the carbazole-derived as fluorophore and boronate moiety as recognition unit. The probe was developed as a turn-off fluorescent chemosensor with fast, high selectivity and sensitivity toward H2O2over other biological reactive oxygen species. What is more, the probe was quenched linear response to H2O2concentration in the range of 1.0×10−8- 2.0×10−5M and lower detection limit down to 6 nM (S / N = 3) was obtained.

The geometric and electronic structures, absorption spectra, transporting properties, chemical reactivity indices and electrostatic potentials of the planar three-coordinate organoboron compounds 1-2 and twisted reference compound Mes(3)B, have been investigated by employing density functional theory (DFT) and conceptual DFT methods to shed light on the planarity effects on the photophysical properties and the chemical reactivity. The results show that the planar compounds 1-2 exhibit significantly lower HOMO level than Mes(3)B, owing to the stronger electronic induction effect of boron centers. This feature conspicuously induces a blue shifted absorption for 1, although 1 seemingly possesses more extended conjugation framework than Mes(3)B. Importantly, the reactivity strength of the boron atoms in 1-2 is much lower than that in Mes(3)B, despite the fact that the tri-coordinate boron centers of 1-2 are completely naked. The interesting and abnormal phenomenon is caused by the strong p-π electronic interactions, that is, the empty p-orbital of boron center is partly filled by π-electron of the neighbor carbon atoms in 1-2, which are confirmed by the analysis of Laplacian of the electron density and natural bond orbitals. Furthermore, the negative electrostatic potentials of the boron centers in 1-2 also interpret that they are not the most preferred sites for incoming nucleophiles. Moreover, it is also found that the planar compounds 1-2 can act as promising electron transporting materials since the internal reorganization energies for electron are really small.

Two anionic metal-organic frameworks (MOFs) with 1D mesoporous tubes (1) and chiral mesoporous cages (2) have been rationally constructed by means of a predesigned size-extended hexatopic ligand, namely, 5,5',5''-(1,3,5-triazine-2,4,6-triyl)tris- (azanediyl)triisophthalate (TATAT). Charge neutrality is achieved by protonated dimethylamine cations. Notably, the two MOFs can be used to separate large molecules based on ionic selectivity rather than the size-exclusion effect so far reported in the literature. Owing to the imino triazine backbone and carboxyl groups of the hexatopic ligand, which provide important host-guest interactions, rare solvatochromic phenomena of 1 and 2 are observed on incorporating acetone and ethanol guests. Furthermore, guest-dependent luminescence properties of compound 2 were investigated, and the results show that luminescence intensity is significantly enhanced in toluene and benzene, while quenching effects are observed in acetone and ethanol. Thus, compound 2 may be a potential material for luminescent probes.

The geometric and electronic structures and photophysical properties of anilido-pyridine boron difluoride dyes 1-4, a series of scarce 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) derivatives with large Stokes shift, are investigated by employing density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations to shed light on the origin of their large Stokes shifts. To this end, a suitable functional is first determined based on functional tests and a recently proposed index-the charge-transfer distance. It is found that PBE0 provides satisfactory overall results. An in-depth insight into Huang-Rhys (HR) factors, Wiberg bond indices, and transition density matrices is provided to scrutinize the geometric distortions and the character of excited states pertaining to absorption and emission. The results show that the pronounced geometric distortion due to the rotation of unlocked phenyl groups and intramolecular charge transfer are responsible for the large Stokes shift of 1 and 2, while 3 shows a relatively blue-shifted emission wavelength due to its mild geometric distortion upon photoemission, although it has a comparable energy gap to 1. Finally, compound 4, which is designed to realize the rare red emission in BODIPY derivatives, shows desirable and expected properties, such as high Stokes shift (4847 cm(-1)), red emission at 660 nm, and reasonable fluorescence efficiency. These properties give it great potential as an ideal emitter in organic light-emitting diodes. The theoretical results could complement and assist in the development of BODIPY-based dyes with both large Stokes shift and high quantum efficiency.

When the oligothiophene is substituted by dicyanovinyl (DCV) or tricyanovinyl (TCV) group, how does its transport property change? Here, we will mainly focus on exploring the influence on charge transport properties of introducing a strong electron-withdrawing DCV/TCV group to the thiophene units within Marcus–Levich–Jortner formalism at the level of density functional theory. The results show that the introduction of cyanovinyl-substituents improves the molecular π-stacking, decreases the frontier molecular orbital energy levels and reorganization energies, and increases the transfer integrals and mobilities, comparing with their parent thiophene molecules. It is interesting to find the phenomenon that enriching intermolecular interactions can be favorable for controlling the transport channel and thus get high mobility, which would be shown by the angular resolution anisotropic mobilities analysis. Besides, the simulated packing motifs of dimers for 3a and 3b without crystal structures reported indicate that their packing may form the slip π–π stacking, and that 3b may be a good ambipolar material. In a word, compared with corresponding thiophene analogues and tetracyanoquinodimethane, these compounds may become the candidates for the n-type or ambipolar organic semiconductor materials.

Phosphole-based systems due to the unique electronic and optical properties have recently been paid much attention as optoelectronic materials. In this work, the relationship among the electronic structure, charge injection, and transport was investigated for five derivatives of dithieno[3,2-b:2′,3′-d]phosphole (systems 1–5). The structures of systems 1–5 in the ground (S0) and the lowest singlet excited (S1) states were optimized at the HF/6-31G* and CIS/6-31G* levels of theory, respectively. Based on these structures, electronic spectra were calculated by time-dependent density functional theory. The simulated emission peaks of five phosphole derivatives locating at the blue–green region (448–516 nm), are in good agreement with the experimental data. Compared with tris-(8-quinolinolate) aluminum (III) (Alq3), normally used as an excellent electron transporter, systems 1–5 show a significant improvement in electron affinity (EA) due to σ*–π* hyperconjugation, which can effectively promote ability of electron injection. The small differences between λ h and λ e for systems 1–5 (0.06–0.14 eV) facilitate charge transfer balance, which suggests systems 1–5 can act as potential ambipolar materials. Owing to good rigidity, low-lying LUMO levels, delocalized frontier molecular orbitals, and the small reorganization energies, the five derivatives of dithieno[3,2-b:2′,3′-d]phosphole are expected to be high-efficiency blue materials in single-layer OLEDs.

In this study, comparative proteomics was used to investigate the interaction of Spodoptera exigua and Arabidopsis thaliana. By using 2-D electrophoresis of differentially expressed proteins, combined with high-throughput matrix-assisted laser desorption/ionization time of flight mass spectrometry (MALDI-TOF MS) and MALDI-TOF/TOF MS, the changes in the abundance of proteins induced by insect feeding were studied in A. thaliana. More than 1,100 protein spots were reproducibly detected on each gel. The intensities of 30 protein spots in particular changed significantly, showing differences in volume of at least twofold. Among these, 17 protein spots were upregulated, and 13 were downregulated following an 8-h insect feeding period. Nineteen insect-feeding-responsive proteins were identified, all of which were involved in metabolic regulation, binding functions or cofactor requirement of protein, cell rescue, and defense and virulence, as assessed by Munich Information Center for Protein Sequences function category. About 50% of these were involved in metabolism, including transketolase, S-adenosylmethionine synthase 3, 2,3-biphosphoglycerate-independent phosphoglycerate mutase, beta-ureidopropionase, GDP-d-mannose 3′,5′-epimerase, and fatty acid synthase. The identification of insect-feeding-responsive proteins on Arabidopsis provides not only new insights into insect stress but also a good start for further investigation of their functions. Understanding how the plant responses to insects in the proteomic level will provide tools for a better management of insect pest in the field.