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Detailed photophysical processes of two AuCu 14 clusters with different substituents (-F or -C(CH 3 ) 3 ) of the thiol ligand were studied in this work. The electronic effect of the substituents led to structural shrinkage, thus enhancing the luminous intensity. The internal conversion (IC) and intersystem crossing (ISC) rates in the AuCu14-C(CH3)3 crystal were slower compared with the AuCu14-F crystal, which was caused by the steric effect.

Chiral 2D organic-inorganic hybrid perovskites (C-2D-OIHPs) with circularly polarized luminescence (CPL) have important promising applications in optical, electronic, and chiroptoelectronic devices. Herein, we report enantiomeric crystals of R / S -FMBA) 2 PbBr 4 . (FMBA = 4-fluorophenethylamine), which demonstrated bright room-temperature CPL emission. For the first time, the oriented films along the c -axis of this pair of C-2D-OIHPs exhibited a 16-fold increase in the asymmetry factors of absorbance ( g CD ) and a 5-fold rise in the asymmetry factors of CPL ( g lum ), reaching up to ± 1 × 10 -2 .

Introducing sulfonic acid groups into MOF materials is one of the effective approaches to enhance proton conduction. Here, we attempted to prepare a new post-modified ZIF-90-based material by addition reaction of the aldehyde group with bisulfite to obtain partially functionalized ZIF-90-SO 3 Na (2.3) . ZIF-90-SO 3 Na (2.3) exhibits a high proton conductivity of 2.26 × 10 -2 S cm -1 at 98% RH and 100 °C.

It has been demonstrated that polyoxometalates (POMs) have strong anchoring abilities with efficient catalysis of lithium polysulfides (LiPSs). However, the severe aggregation that buries the effective active sites of POMs along with poor electrical conductivity limits the practical application of POMs in lithium sulfur batteries (LSBs). In our strategy, we utilized reduced graphene oxide (rGO) to support a POM catalyst entrapped in a MIL-88A(FeCo) network with a hollow shell skeleton as the sulfur host material. H 4 PW 11 VO 40 (PW 11 V) with optimal vanadium atom implantation ensures the ruggedness and integrity of the hollow structure, which is conducive to achieving high sulfur loading as well as accommodating the volume change of the sulfur cathode during the charging and discharging process. Importantly, PW 11 V can capture polysulfides through firm chemical adsorption and accelerate redox reactions of LiPS conversion by effective electrochemical catalysis. Furthermore, the satisfactory electrical conductivity of rGO provides access for electrons to reach the interface of PW 11 V and polysulfides and trigger Li-S conversion reactions. Thus, the constructed PW 11 V-based sulfur cathode exhibited a superior specific capacity of 905 mA h g -1 after 100 cycles under 0.2 C and long cycling life with a capacity recession rate of 0.046% for each cycle upon 500 cycles under 3 C. This research reveals the effect of vanadium atom substitution of POMs on the cycling performance of a sulfur cathode and affords insight for developing high-performance LSBs.

Nanoclusters (NCs) are considered as initial states of condensed matter, and unveiling their formation mechanism is of great importance for directional synthesis of nanomaterials. Here, we initiate the reaction of Ag(i) ions under weak reducing conditions. The prolonged reaction period provides a unique opportunity for revealing the five stages of the growth mechanism of 20-electron superatomic Ag 70 NCs by a time-dependent mass technique, that is, aggregate (I) → reduction (II) → decomposition and recombination (III) → fusion (IV) → surface recombination and motif enrichment (V), which is different from the formation process applicable to the gold clusters. More importantly, the key intermediates, Ag 14 without free electrons (0e) in the first (stage I) and Ag 24 (4e) in the second (stage II), were crystallized and structurally resolved, and the later transformation rate towards Ag 70 was further controlled by modulating solvents for easy identification of more intermediates. In a word, we establish a reasonable path of gradual expansion in size and electrons from Ag(i) ions to medium-sized 20e Ag 70 . This work provides new insights into the formation and evolution of silver NCs, and unveils the corresponding optical properties along with the process., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

A new Ag 36 nanocluster with a closed electronic structure and eight valence electrons is reported, which has a similar structure to that of an open-shell Ag 34 nanocluster with three valence electrons, except that in the shell two (Ag-PPh 3 ) + cations replace two S 2- anions specifically. The fine structural modulation leads to various levels of activity for singlet oxygen photogeneration due to the distinct optical gaps of the nanoclusters.

A cationic COF (CCOF) was imported to afford stable proton conductive material while the positively charged CCOF can constrain the inorganic anion groups into the framework through an ion exchange process. The inorganic anions could play the role of proton donors to provide a rich source of protons, as well as the proton acceptors for proton transmission, thus forming an interlinked proton conduction pathway within the framework. The proton conductivities of COF materials loaded with different anions have been improved to varying degrees, and the conductivity of H 2 PO 4 - @CCOF is up to 3.86 × 10 -2 S cm -1 at 100 °C.

In this work, organic supramolecular linkers involving cucubit[6]urils CB[6] and N , N '-hexamethylene-bis(pyrazinyl hexafluorophosphate) (BPHF@CB[6]) were utilized to assemble dodenuclear silver chalcogenolate clusters into three one-dimensional (1D) materials under different synthesis conditions. These three crystal structures of CB[6]-based sliver cluster-organic rotaxane frameworks were well resolved, and their emission properties were investigated systematically. This construction strategy involving organic supramolecular linkers gives a new methodology for cluster-assembled materials with intriguing structural and functional properties.

Here, we evaluate photocatalytic H 2 generation of three stable Cu-based coordination polymers (CPs), where each two-coordinated Cu(i) is stabilized in interchain -[Cu-imidazole(R)-Cu]- units. Importantly, a record-high H 2 evolution rate of 57.64 mmol g -1 h -1 is identified for Cu-MIM. Theoretical calculations reveal that the excellent catalytic performances are due to the delicate synergies of the inter-chain double-site Cu atoms.

A new hexanuclear silver(i) cluster (NC-Ag6) that emits bright-blue phosphoresce with a lifetime of 22.4 μs and a quantum yield (QY) of 22% under ambient conditions was synthesized. A film combining NC-Ag6 with yellow cerium(iii)-doped yttrium aluminum garnet phosphors (YAG:Ce3+) displays "chameleon"-like emission (including white), which is related to excitation-dependent Förster resonance energy transfer (FRET) between dual phosphors. The mechanoresponsive luminescence colour of this silver cluster ranges from blue to green virtually without loss of QY.

Silver chalcogenide wires are assembled for the first time using a linear fluorinated carboxylate ligand into a metal-organic framework (MOF) with multifunctional properties. Fluorinated ligands in the host framework endow the MOF with excellent hydrophobicity. More interestingly, it displays typical semiconductivity due to the ordered nanoarray of non-discrete helical (-Ag-S-)n chains.

The present study reports the fabrication of a silver chalcogenolate cluster hybrid membrane (SCC membrane) through self-assembly of SCCs, and then covalent cross-linking of the modified SCC assembled materials. This strategy provides access to silver clusters with superior chemical stability and enhanced luminescence efficiency for practical applications.

In the present paper, an efficient approach for the construction of 1, N 6 -ethenoadenines from conveniently prepared N 6 -propargyl-adenines is developed. This reaction merges N -iodosuccinimide radical initiation and aerobic aminooxygenation in dioxane. This mild, 5-exo-dig , and metal-free cascade reaction could be applied to a wide substrate scope to provide 1, N 6 -ethenoadenines in moderate to good yields. The reaction mechanism was proposed and tested using radical inhibitor (butylated hydroxytoluene) and isotopic labelling ( 18 O 2 ) experiments., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The [Mn 2 Cl 9 ] 5- mode of red emissive (C 4 NOH 10 ) 5 Mn 2 Cl 9 ·C 2 H 5 OH under thermal treatment will be cleaved into [MnCl 4 ] 2- in the green emissive (C 4 NOH 10 ) 2 MnCl 4 with the departure of ethanol. The rapid conversion of luminescence from red to green provides new insight into the luminescence origin and thermal stability of organic-inorganic metal halide hybrids.

Two water-stable silver(i) cation metal organic frameworks (MOFs), namely 2D MOF {[Ag(L) 2 ]BF 4 } n (1) and 3D MOF {[Ag 3 (L) 3 ]·(H 2 O)·(CF 3 SO 3 ) 3 } n (2) (L = 1-(4-aminobenzyl)-1,2,4-triazole), have been prepared. 1 is the first example of a 2D MOF-based sensor for real-time discrimination of l- and d-cysteine from other amino acids through the quenching effect. Through deliberately tuning the nanoparticles of 2 under ultrasound conditions, these nanoparticles are, for the first time, successfully applied as an excellent DNA detecting platform.

The interactions between water molecules and aromatic rings are known to be common and important in physics, chemistry and life sciences. Benzene-water complexes are the main prototype systems for O-Hπ and lone-pair (lp)π interactions in theoretical research, however solid state examples are very rare. Here, the solid state example of water sandwiched by a pair of aromatic rings is observed in a silver-mellitate framework, where lpπ and O-Hπ interactions coexist. The coexistence of these two interactions has been further verified by theoretical calculations. In addition, ammonium ions and water molecules as proton sources, and strongly H-bonded nets as the pathway of proton transport, make the reported MOFs (metal-organic frameworks) exhibit distinct proton conduction.

Reactions of lanthanide nitrate, 1,3,5-benzenetrisbenzoic acid (H3BTB) and [RMI]Br ionic liquids (RMI = 1-alkyl-3-methylimidazolium; R = ethyl, propyl, butyl, amyl, or hexyl), gave rise to two novel lanthanide metal-organic frameworks (Ln-MOFs) [Ln(BTB)H2O], where Ln = Eu , Tb . In addition to helping solubilise the starting materials under the reaction conditions there is evidence that [RMI]Br itself can play a structure directing role and is intimately involved in template ordering in [Ln(BTB)H2O], even though neither the [RMI](+) cation nor the Br(-) anion is occluded into the ultimate structure. and are isostructural and consist of infinite rod-shaped lanthanide-carboxylate building units which are further bridged by trigonal-planar BTB ligands to give noninterpenetrated open 3D frameworks featuring a (6,6)-connected topology with the point symbol (4(4)·6(7)·8(4))(4(8)·6(7)). Importantly, the strong emission of and dispersed in water prompted us to explore their application for detection of different nitroaromatics in an aquatic system. and show similar selectivity and sensitivity towards the presence of trace amounts of nitroaromatic analytes in the aqueous phase, showing potential as explosive sensors.

The ordered dimethylammonium cations [H2N(CH3)2](+) and helical water spirals as guest species make a super water stable europium-organic framework possess a proton conductivity of over 10(-3) S cm(-1) at 68% relative humidity. A fluorescent probe for Fe(3+) and Cu(2+) ions via a different mechanism has also been realized.

A new tetranuclear Cu4(μ3-OH)2-based metal-organic framework (MOF) with sulfonate-carboxylate ligands features large hydrophilic channels. This MOF exhibits proton conductivity over 10(-3) S cm(-1) at 85-100 °C and 98% relative humidity and colossal dielectric constant.

A new photoelectrochemical immunoassay for prostate-specific antigen (PSA) was successfully developed with high sensitivity via immunogold labeling., (This journal is © The Royal Society of Chemistry 2012)

An innovative strategy of fabricating electrode material by layered assembling two kinds of one-atom-thick sheets, carboxylated graphene oxide (GO) and Co-Al layered double hydroxide nanosheet (Co-Al LDH-NS) for the application as a pseudocapacitor is reported. The Co-Al LDH-NS/GO composite exhibits good energy storage properties.