Search

Fluorescence imaging in the second near-infrared window (NIR-II, 1000-1700 nm) using small-molecule dyes is highly potential for clinical use. However, many NIR-II dyes suffer from the emission quenching effect and extremely low quantum yields (QYs) in the practical usage forms. The AIE strategy has been successfully utilized to develop NIR-II dyes with donor-acceptor (D-A) structures with acceptable QYs in the aggregate state, but there is still a large room for QY improvement. Here, we rationally designed NIR-II emissive dye named TPE-BBT and its derivative (TPEO-BBT) by changing the electron-donating triphenylamine unit to tetraphenylethlene (TPE). Their nanoparticles exhibited ultrahigh relative QYs of 31.5% and 23.9% in water, respectively. By using an integrating sphere, the absolute QY of TPE-BBT nanoparticles was measured to be 1.8% in water. Its crystals showed an absolute QY of 10.4%, which is the highest value among organ-ic small molecules reported so far. The optimized D-A interaction and the higher rigidity of TPE-BBT in the aggregate state are believed to be the two key factors for its ultrahigh QY. Finally, we utilized TPE-BBT for NIR-II photoluminescence (PL) and chemiluminescence (CL) bioimaging through successive CL resonance energy transfer and Förster resonance energy transfer processes. The ultrahigh QY of TPE-BBT realized an excellent PL imaging quality in mouse blood vessels, and an excellent CL imaging quality in the local arthrosis inflammation in mice with a high signal-to-background ratio of 130. Thus, the design strategy presented here brings new possibilities for the development of bright NIR-II dyes and NIR-II bioimaging technologies.

Asymmetric synthesis of chiral pyrrolidines bearing an all-carbon quaternary stereocenter in the 3-position remains challenging. Herein we report two efficient protocols by means of oxetane desymmetrization, featuring the use of a readily available

Long-persistent luminescence (LPL), also known as afterglow, is a phenomenon in which the material shows long-lasting luminescence after the cessation of the excitation source. The research of LPL continues to attract much interest due to its fundamental nature and its potential in the development of the next generation of functional materials. However, most of the current LPL materials are multicomponent inorganic systems obtained after harsh synthetic procedures and often use rare-earth metals. Recently, metal free organic long-persistent luminescence (OLPL) has gained much interest because it can bypass many of the disadvantages of inorganic systems. To date, the most successful method to generate OLPL systems is to access charge-separated states through binary donor-acceptor exciplex systems. However, it has been reported that the ratios of the binary systems affect OLPL properties, complicating the reproducibility and large-scale production of OLPL materials. Simpler OLPL systems can overcome these issues for the benefit of the development and adoption of OLPL systems. Here, we report on the rational design and synthesis of a single-component OLPL system with detectable afterglow for at least 12 min under ambient conditions. This work exemplifies an easy design principle for new OLPL materials. The investigation of the material provides valuable insights toward the generation of OLPL from a single-component system.

The combination of chirality and semiconducting properties has enabled chiral metal-halide semiconductors (MHS) to be promising candidates for spin- and polarization-resolved optoelectronic devices. Although several chiral MHS with rich chemical and structural diversity have been reported lately, the macroscopic origin of chiroptical activity remains elusive. Here, combining spectroscopic measurements and Mueller matrix analysis, we discover that the previously reported "apparent" anisotropy factor measured from circular dichroism (CD) in chiral MHS thin films is not an intrinsic chiroptical property, but rather, arising from an interference between the film's linear birefringence (LB) and linear dichroism (LD). We verify the presence of LB and LD effects in both one-dimensional and zero-dimensional chiral MHS thin films. We establish spectroscopic methods to decouple the genuine CD from other spurious contributions, which allows a quantitative comparison of the intrinsic chiroptical activity across different chiral MHS. The relationship between the structure and the genuine chiroptical activity is then uncovered, which is well described by the chirality-induced spin-orbit coupling in the chiral structures. Our study unveils the macroscopic origin of chiroptical activity of chiral MHS and provides design principles for obtaining high anisotropic factors for future chiral optoelectronic applications.

Due to the fast dynamics and re-equilibration of supramolecular self-assembly, bottom-up molecular strategies to fabricate well-defined and controllable multiblock structures are rare. Herein, we propose a new concept for fabrication of fluorescent multiblock microcolumns containing 1 to 7 blocks via hierarchical supramolecular self-assembly based on cucurbit[8]uril (CB[8]), NaBr and an AIEgen guest. Through the complexation between CB[8] and different numbers of AIEgen guests (2, 1, 0), the competitive displacement caused by the binding of the sodium cation to the CB[8] portal, and the reversible assembly of positively charged guests in salt solutions, one-pot hierarchical supramolecular self-assembly is realized. The molecular structure of each block is analyzed by single-crystal X-ray diffraction. The AIEgen enables the self-assembly of multiblocks to be visualized, understood, and regulated.

Solid-state molecular motions (SSMM) play a critical role in adjusting behaviors and properties of materials. However, research on SSMM, especially for multicomponent systems, suffers from various problems and is rarely explored. Herein, through collaboration with cocrystal engineering, visualization and manipulation of SSMM in two-component systems, namely, FSBO ((E)-2-(4-fluorostyryl)benzo[d]oxazole)/TCB (1,2,4,5-tetracyanobenzene) and PVBO ((E)-2-(2-(pyridin-4-yl)vinyl)benzo[d]oxazole)/TCB, were realized. The obtained yellow-emissive F/T (FSBO/TCB) cocrystal displayed turn-on fluorescence, and the green-emissive P/T (PVBO/TCB) cocrystal presented redder emission, both of which exhibited an aggregation-induced emission property. At varied pressure and temperature, the grinding mixtures of FSBO/TCB and PVBO/TCB displayed different molecular motions that were readily observed through the fluorescence signal. Notably, even without grinding, FSBO and TCB molecules could move over for 4 mm in a 1D tube. The unique emission changes induced by SSMM were applied in information storage and dynamic anticounterfeiting. This work not only visualized and manipulated SSMM but offered more insights for multicomponent study in aggregate science.

Life process is amazing, and it proceeds against the eternal law of entropy increase through molecular motion and takes energy from the environment to build high-order complexity from chaos to achieve evolution with more sophisticated architectures. Inspired from the elegance of life process and also to effectively exploit the undeveloped solid-state molecular motion, two unique chiral Au(I) complexes were elaborately developed in this study, in which their powders could realize a dramatic transformation from nonemissive isolated crystallites to emissive well-defined microcrystals under the stimulation of mechanical force. Such an unusual crystallization was presumed to be caused by molecular motions driven by the formation of strong aurophilic interactions as well as multiple C-H···F and π-π interactions. Such a prominent macroscopic off/on luminescent switching could also be achieved through extremely subtle molecular motions in the crystal state and presented a filament sliding that occurred in a layer-by-layer molecular stacking fashion with no involvement of any crystal phase transition. Additionally, it had been demonstrated that the manipulation of the solid-state molecular motions could result in the generation of circularly polarized luminescence.

We report in this communication the first example of catalytic alkyne metathesis reactions mediated by well-defined non-d0 alkylidyne complexes. The air-stable d2 Re(V) alkylidyne complex Re4, bearing two PO-chelating ligands and a labile pyridine ligand, could catalyze homometathesis of internal alkynes with a broad substrate scope, including alcohols, amines, and even carboxylic acids. The catalyst can tolerate heating, air, and moisture in both solid and solution states, and the catalytic metathesis reactions could proceed normally in wet solvents.

Gold(I) N-heterocyclic carbene (AuI -NHC) complexes have emerged as potential anticancer agents owing to their high cytotoxicity and stability. Integration of their above unique functions with customized aggregation-induced emission (AIE) luminogens to achieve specific bioimaging and efficient theranostics to cancer is highly desirable but is rarely studied. Now, a series of novel AuI -NHC compounds were developed with AIE characteristics. A complex with a PPh3 ligand was selected out as it could achieve both prominent specific imaging of various cancer cells and efficient inhibition of their growth with negligible toxic effects on normal cells due to the targeting binding and strong inhibition towards thioredoxin reductase. This complex could also act as a powerful radiosensitizer to boost the anticancer efficacy with performance superior to that of popularly used auranofin. It holds great potential as a specific and effective theranostic drug in cancer diagnosis and precise therapy.

A family of d

Organic near-infrared (NIR) luminogens have attracted intensive attention considering their vast potential applications in areas like bioimaging, organic light-emitting diodes (OLEDs) and night-vision telecommunication. However, organic NIR luminogens with high solid quantum efficiencies are scarce, limiting their applications. Here, we reported an electron-deficient acceptor, BSM, based on dithiafulvalene and benzothiadiazole, which could work as a strong acceptor to produce highly efficient NIR emitters with aggregation-induced emission (AIE) property. One of the AIEgens, TBSMCN emitted at 820 nm with a solid quantum yield of 10.7 %. When applied to solution-processed OLEDs, an outstanding external quantum efficiency (EQE) of 9.4 % was achieved with a peak wavelength at 728 nm. Moreover, its non-doped device could achieve an extraordinary EQE of 2.2 % peaking at 804 nm. In the further optimized configuration, when an extra sensitizer was added to harvest triplet excitons, the EQE unprecedentedly soared up to 14.3 % with a peak wavelength of 750 nm.

Dewar benzenes, the metastable valence isomers of benzenes, have been extensively studied both experimentally and theoretically. In contrast, little is known about Dewar metallabenzenes having a transition metal in the skeletal framework, despite the recent intensive interest in the development of chemistry of metallabenzenes. Herein, we report the isolation and characterization of the first examples of structurally characterized Dewar metallabenzenes. These compounds were generated via unprecedented reactions of metallacyclobutadienes with aminoalkynes.

Supramolecular macrocyclic hosts have long been used in smart materials. However, their triplet emission and regulation at crystal level is rarely studied. Herein, ultralong and universal room-temperature phosphorescence (RTP) is reported for traditional crown ethers. A supramolecular strategy involving chain length adjustment and morphological locking through complexation with K+ was explored as a general method to tune the phosphorescence lifetime in the solid state. A maximum 10-fold increase of lifetime after complex formation accompanied with by invisible to visible phosphorescence was achieved. A deep encryption based on this activated RTP strategy was also facilely fabricated. This work thus opens a new world for supramolecular macrocycles and their intrinsic guest responsiveness offers a new avenue for versatile smart luminescent materials.

We have studied the photophysics of tetrafurylethene, an aggregation-induced emission luminogen with exceptionally short intramolecular O-O distances of 2.80 Å and a significant red-shifted morphochromism (27 nm) when going from the aggregate to the crystal. The short O-O distances, which are substantially smaller than the sum of the van der Waals radii (3.04 Å), are due to the fact that the oxygen atoms act as an electronic bridge connecting the furan rings on opposite ends of the central double bond, giving rise to a circular delocalization of the π-electron density across the rings. In the excited state the O-O distance is further reduced to 2.70 Å; the increased O-O interaction causes a narrowing of the HOMO-LUMO gap, resulting in the red morphochromism of the emission. Our results show the structural origin of the red-shifted emission lies in close O-O contacts, paving the way for understanding the clusteroluminescence of oxygen-rich non-conjugated systems that emit visible light.

Molecular motions are essential natures of matter and play important roles in their structures and properties. However, owing to the diversity and complexity of structures and behaviors, the study of motion-structure-property relationships remains a challenge, especially at all levels of structural hierarchy from molecules to macro-objects. Herein, luminogens showing aggregation-induced emission (AIE), namely, 9-(pyrimidin-2-yl)-carbazole (PyCz) and 9-(5-R-pyrimidin-2-yl)-carbazole [R = Cl (ClPyCz), Br (BrPyCz), and CN (CyPyCz)], were designed and synthesized, to decipher the dependence of materials' structures and properties on molecular motions at the molecule and aggregate levels. Experimental and theoretical analysis demonstrated that the active intramolecular motions in the excited state of all molecules at the single-molecule level endowed them with more twisted structural conformations and weak emission. However, owing to the restriction of intramolecular motions in the nano/macroaggregate state, all the molecules assumed less twisted conformations with bright emission. Unexpectedly, intermolecular motions could be activated in the macrocrystals of ClPyCz, BrPyCz, and CyPyCz through the introduction of external perturbations, and synergic strong and weak intermolecular interactions allowed their crystals to undergo reversible deformation, which effectively solved the problem of the brittleness of organic crystals, while endowing them with excellent elastic performance. Thus, the present study provided insights on the motion-structure-property relationship at each level of structural hierarchy and offered a paradigm to rationally design multifunctional AIE-based materials.

Apart from the traditional through-bond conjugation (TBC), through-space conjugation (TSC) is gradually proved as another important interaction in photophysical processes, especially for the recent observation of clusteroluminescence from nonconjugated molecules. However, unlike TBC in conjugated chromophores, it is still challenging to manipulate TSC and clusteroluminescence. Herein, simple and nonconjugated triphenylmethane (TPM) and its derivatives with electron-donating and electron-withdrawing groups were synthesized, and their photophysical properties were systematically studied. TPM was characterized with visible clusteroluminescence due to the intramolecular TSC. Experimental and theoretical results showed that the introduction of electron-donating groups into TPM could red-shift the wavelength and increase the efficiency of clusteroluminescence simultaneously, due to the increased electronic density and stabilization of TSC. However, TPM derivatives with electron-withdrawing groups showed inefficient or even quenched clusteroluminescence caused by the vigorous excited-state intramolecular motion and intermolecular photoinduced electron transfer process. This work provides a reliable strategy to manipulate TSC and clusteroluminescence.

Herein we report a linear ionic molecule that assembles into a supramolecular nano-tunnel structure through synergy of trident-type ionic interactions and π-π stacking interactions. The nano-tunnel crystal exhibits anisotropic guest adsorption behavior. The material shows good thermal stability and undergoes multi-stage single-crystal-to-single-crystal phase transformations to a nonporous structure on heating. The material exhibits a remarkable chemical stability under both acidic and basic conditions, which is rarely observed in supramolecular organic frameworks and is often related to structures with designed hydrogen-bonding interactions. Because of the high polarity of the tunnels, this molecular crystal also shows a large CO2 -adsorption capacity while excluding other gases at ambient temperature, leading to high CO2 /CH4 selectivity. Aggregation-induced emission of the molecules gives the bulk crystals vapochromic properties.

An organocatalytic intermolecular C-C bond formation process leading to the efficient synthesis of chiral β,β-diaryl-α-amino acid derivatives is described. In the presence of a suitable chiral phosphoric acid catalyst, a range of para-hydroxybenzyl alcohols serve as efficient precursors to para-quinone methides and then react with azlactones in 1,6-conjugate addition reactions. The asymmetric control has been carefully optimized together with diastereocontrol enabled by identification of the reversible feature of the C-C bond formation and subsequent inhibition by protection of the free hydroxy group in one pot. Compared with previous approaches, including those with pre-synthesized para-quinone methides, this protocol provides an alternative and complementary step- and pot-economical approach for the synthesis of chiral β,β-diaryl-α-amino acid derivatives.

Multimodality imaging is highly desirable for accurate diagnosis by achieving high sensitivity, spatial-temporal resolution, and penetration depth with a single structural unit. However, it is still challenging to integrate fluorescent and plasmonic modalities into a single structure, as they are naturally incompatible because of significant fluorescence quenching by plasmonic noble-metal nanoparticles. Herein, we report a new type of silver@AIEgen (aggregation-induced emission luminogen) core-shell nanoparticle (AACSN) with both strong aggregated-state fluorescence of the AIEgen and distinctive plasmonic scattering of silver nanoparticles for multimodality imaging in living cells and small animals. The AACSNs were prepared through a redox reaction between silver ions and a redox-active AIEgen, which promoted synergistic formation of the silver core and self-assembly of the AIEgen around the core. The resulting AACSNs exhibited good biocompatibility and high resistance to environmental damage. As a result, excellent performance in fluorescence imaging, dark-field microscopy, and X-ray computed tomography-based multimodality imaging was achieved.

Ionic fluorophores are powerful tools for the study of environmental science and bio-imaging. However, traditional ionic dyes usually require long synthetic steps and suffer from a quenching effect caused by aggregation. A water-soluble ionic aggregation-induced emission luminogen called DBTA is presented, which is readily accessed by a one-step reaction. The switchable emission manipulated by hydrogen bonding provided solid evidence for the restriction of intramolecular motions as the mechanism of aggregation-induced emission. DBTA can not only differentiate solvents with different H-bond donor acidities but also capable of wash-free imaging in living HeLa cells and fish larva.

Reactions of silanes with transition-metal complexes are of interest because their relevance to Si–H bond activation, the structural properties of polyhydrides, and catalytic hydrosilylation reactions. This work presents the results derived from reactions of arylsilanes Ph2SiH2 and PhSiH3 with OsH3Cl(PPh3)3 (1). Reaction of 1 with 1 equiv or excess Ph2SiH2 affords OsH3(SiClPh2)(PPh3)3 (2) or OsH4(SiClPh2)(SiHPh2)(PPh3)2 (3), respectively. These silyl complexes are formed via the oxidative addition of Si–H bonds and H/Cl exchange via silylene intermediates. Similarly, reaction of 1 with excess PhSiH3 produced the analogous bis(silyl) complex OsH4(SiClHPh)(SiH2Ph)(PPh3)2 (4). The bis(silyl) complexes are dodecahedral tetrahydride complexes containing weak Si···H interactions. The complex 3 reacts with PPh3 and CH3CN to selectively eliminate Ph2SiH2. Computational studies show that the preference for reductive eliminations from 3 follows the order Ph2SiH2 > H2 > Ph2SiHCl > Ph2HSi-SiClPh2.

Pathogen infection and cancer are the two major human health problems. In this work, we achieved an organic salt photosensitizer (PS), called 4TPA-BQ with aggregation-induced emission feature via one-step reaction. Owing to the aggregation-induced reactive oxygen species generation effect and sufficient small ΔEST, 4TPA-BQ shows a satisfactorily high 1O2 generation efficiency of 97.8%. In vitro and in vivo experiments confirmed that 4TPA-BQ exhibited potent photodynamic antibacterial performance against ampicillin-resistant Escherichia coli with good biocompatibility in a short time (15 min). When the incubation time persisted long enough (12 h), cancer cells were ablated efficiently, leaving normal cells essentially unaffected. This is the first reported time-dependent fluorescence-guided photodynamic therapy in one individual PS for ordered and multiple targeting by varying the external conditions. This can update the design principle of efficient PSs in potential clinical applications.

Polymers containing rich chalcogen elements are rarely reported due to the lack of facile synthesis methods. Herein, a novel multicomponent polymerization route toward chalcogen-rich polymers was introduced. A series of poly(vinyl sulfones) (PVSs) were synthesized at room temperature using readily prepared monomers. PVSs were generated with high regio- and stereo-selectivity in high yields (up to 92.3%). Rich chalcogen elements endowed PVSs with distingctive multifunctionalities. The PVSs possessed good solubility and film-forming ability. Their thin films exhibited outstanding refractive indices up to 1.8062 at 550.0 nm together with good optical transparency in the visible region. Thin films of some polymers can also be fabricated into well-resolved fluorescent photopatterns by photolithography. Thanks to the unique redox properties of selenium, postmodification by oxidation reaction of P1a/2/3a successfully eliminates the caused heavy atom effect and endow resulting polymers with novel functionality as fluorescent bioprobes for cellular imaging.

Acrylonitriles with aggregation-induced emission (AIE) characteristics have been found to show promising applications in two-photon biomedical imaging. Generally, elaborate synthetic efforts are required to achieve different acrylonitriles with distinct functionalities. In this work, we first reported the synthesis of two different group-functionalized AIE-active acrylonitriles (TPAT-AN-XF and 2TPAT-AN) obtained simply by mixing the same reactants at different temperatures using a facile and transition metal-free synthetic method. These two AIE luminogens (AIEgens) exhibit unique properties such as bright red emission in the solid state, large Stokes shift, and large two-photon absorption cross section. Water-soluble nanoparticles (NPs) of 2TPAT-AN were prepared by a nanoprecipitation method. In vitro imaging data show that 2TPAT-AN NPs can selectively stain lysosome in live cells. Besides one-photon imaging, remarkable two-photon imaging of live tumor tissues can be achieved with high resolution and deep tissue penetration. 2TPAT-AN NPs show high biocompatibility and are successfully utilized in in vivo long-term imaging of mouse tumors with a high signal-to-noise ratio. Thus, the present work is anticipated to shed light on the preparation of a library of AIE-active functionalized acrylonitriles with intriguing properties for biomedical applications.

International audience; A combined experimental and theoretical investigation on the cerium(IV) oxo complex [(L-OEt)(2)Ce(=O)(H2O)].MeC(O)NH2 (1; L-OEt(-)=[Co(eta(5)-C5H5){P(O)(OEt)(2)}(3)](-)) demonstrates that the intermediate spin-state nature of the ground state of the cerium complex is responsible for the versatility of its reactivity towards small molecules such as CO, CO2, SO2, and NO. CASSCF calculations together with magnetic susceptibility measurements indicate that the ground state of the cerium complex is of multiconfigurational character and comprised of 74 % of Ce-IV and 26 % of Ce-III. The latter is found to be responsible for its reductive addition behavior towards CO, SO2, and NO. This is the first report to date on the influence of the multiconfigurational ground state on the reactivity of a metal-oxo complex.

The 12-membered-ring metallacycles [mer-Re{≡CCH=C(R)C≡C-}Cl(PMe2 Ph)3 )]2 (R=CMe3 , 1-adamantyl), which are organometallic analogues of antiaromatic octadehydro[12]annulene, are prepared by heating the methyl carbyne complexes mer-Re{≡CCH=C(R)C≡CH}(CH3 )Cl(PMe2 Ph)3 . An intermolecular σ-bond metathesis between the Re-CH3 bond and the acetylenic C-H bond is proposed for their formation.

Treatment of CpRuH(PP) (PP=dppm, dppe) with TlPF6 produced [CpRu(H)(Tl)(PP)]PF6 . X-ray diffraction and computational studies suggest that the complexes contain a Ru-H-Tl 3c-2e bond and can be viewed as the first σ-complexes of period 6 main-group hydrides [CpRu{η2 -(H-Tl)}(PP)]PF6 or [Tl{η2 -H-RuCp(PP)}]PF6 . The complexes can be stored as a solid at room temperature for days without appreciable decomposition, but are unstable in solution and evolved to the trimetallic complexes [{CpRu(PP)}2 (μ-Tl)]PF6 .

Heterometallic Ce(IV)/M (M = Mo(VI), Re(VII), V(V)) oxo clusters supported by the Kläui tripodal oxygen ligand [(η(5)-C5H5)Co{P(O)(OEt)2}3](-) (LOEt(-)) have been synthesized and structurally characterized, and the catalytic activity of the Ce(IV)/V(V) oxo cluster in the oxidation of thioanisoles has been studied. Treatment of [Ce(LOEt)Cl3] (1) with [Ag2MoO4] afforded the reported Ce(IV)/Mo(VI) cluster [H4(CeLOEt)6Mo9O38] (2), whereas that with [AgReO4] yielded the Ce(IV)/Re(VII) cluster [{LOEtCe(ReO4)2(H2O)(μ-ReO4)}2] (3) that contains an 8-membered Ce2Re2O4 ring. Treatment of 1 with [Ag3VO4] afforded the Ce(IV)/V(V) cluster [H2(CeLOEt)4(V[double bond, length as m-dash]O)4(μ4-O)(μ3-O)12] (4) containing a {Ce4V4O13} oxo-metallic core. The solid-state structure of 4 consists of four {VO4}(3-) units bridged by four {LOEtCe(3+)} moieties and a μ4-oxo ligand. Each Ce atom in 4 is 9-coordinated, whereas the geometry around each V atom is pseudo square pyramidal with a terminal oxo at the apical position. Cluster 4 is an active catalyst for the oxidation of substituted thioanisoles with tert-butyl hydroperoxide. For example, the oxidation of thioanisole with tert-butyl hydroperoxide in the presence of 0.01 mol% of 4 gave a ca. 30 : 1 mixture of the sulfoxide and sulfone products in 96% yield.

We present a nitrogen-containing polycyclic aromatic hydrocarbon (N-PAH), namely 12-methoxy-9-(4-methoxyphenyl)-5,8-diphenyl-4-(pyridin-4-yl) pyreno[1,10,9-h,i,j]-isoquinoline (c-TPE-ON), which exhibits high quantum-yield emission both in solution (blue) and in the solid state (yellow). This molecule was unexpectedly obtained by a three-fold, highly regioselective photocyclodehydrogenation of a tetraphenylethylene-derived AIEgen. Based on manifold approaches involving UV/Vis, photoluminescence, and NMR spectroscopy as well as HRMS, we propose a reasonable mechanism for the formation of the disk-like N-PAH that is supported by density functional theory calculations. In contrast to most PAHs that are commonly used, our system does not suffer from entire fluorescence quenching in the solid state due to the peripheral aromatic rings preventing p-p stacking interactions, as evidenced by single-crystal X-ray analysis. Moreover, its rod-like microcrystals exhibit excellent optical waveguide properties. Hence, c-TPE-ON comprises a N-PAH with unprecedented luminescent properties and as such is a promising candidate for fabricating organic optoelectronic devices. Our design and synthetic strategy might lead to a more general approach to the preparation of solution-and solid-state luminescent PAHs.

Bis(mandelato)borate [B(Man)2](-) (R- or S-) anions are simply prepared and appear widely effective for resolution of racemic cations. Three examples demonstrate their scope; the alkaloid tetrahydropalmatine (THP), 1,2-diaminopropane (1,2-dap) and the metal-organic complex [Co(phen)3](3+) are readily resolved, either by a facile one-pot procedure, or via counter-ion metathesis.

π-Bonds connected with aromatic rings were generally believed as the standard structures for constructing highly efficient fluorophores. Materials without these typical structures, however, exhibited only low fluorescence quantum yields and emitted in the ultraviolet spectral region. In this work, three molecules, namely bis(2,4,5-trimethylphenyl)methane, 1,1,2,2-tetrakis(2,4,5-trimethylphenyl)ethane, and 1,1,2,2-tetraphenylethane, with nonconjugated structures and isolated phenyl rings were synthesized and their photophysical properties were systematically investigated. Interestingly, the emission spectra of these three molecules could be well extended to 600 nm with high solid-state quantum yields of up to 70%. Experimental and theoretical analyses proved that intramolecular through-space conjugation between the “isolated” phenyl rings played an important role for this abnormal phenomenon.

Whereas terminal oxo complexes of transition and actinide elements are well documented, analogous lanthanide complexes have not been reported to date. Herein, we report the synthesis and structure of a cerium(IV) oxo complex, [CeO(LOEt )2 (H2 O)]⋅MeC(O)NH2 (1; LOEt (-) =[Co(η(5) -C5 H5 ){P(O)(OEt)2 }3 ](-) ), featuring a short CeO bond (1.857(3) Å). DFT calculations indicate that the hydrogen bond to cocrystallized acetamide plays a key role in stabilizing the CeO moiety of 1 in the solid state. Complex 1 exhibits oxidizing and nucleophilic reactivity.

A new synthetic route to nitrogen-rich hyperbranched polymers is developed. The polycyclotrimerizations of dinitriles [NC–C6H4–O(CH2)4O–C6H4–CN and NC–C6H4–O(CH2)4O–Ar–O(CH2)4O–C6H4–CN Ar = isopropylidenebis(1,4-phenylene), 9,9-fluorenylenebis(1,4-phenylene) and 1,2-diphenylethenylenebis(1,4-phenylene)] catalyzed by trifluoromethanesulfonic acid proceed smoothly in 1,2-dichlorobenzene at room temperature, affording hyperbranched poly(triazine)s with high degree of branching (DB ∼63%) in high yields (up to 74.7%). All the polymers are soluble and film-forming. The polymers are thermally and morphologically stable, showing high thermal-degradation and glass-transition temperatures up to 363 and 126.5 °C, respectively. They are optically transparent, allowing almost all visible and IR lights to transmit through. The polymer thin films show high refractive indices (n = 1.7456–1.5857) in a wide spectral region (400–1600 nm) as well as high Abbe numbers (νD′ up to 187.4) and low optical dispersions (D′ down to ...

Reactions of [ReH(5)(PMe(2)Ph)(3)] with alkynols HC≡CC(OH)(R)C≡CSiMe(3) (R=tBu, iPr, 1-adamantyl) in the presence of HCl give the vinylcarbyne complexes [Re{≡CCH=C(R)C≡CSiMe(3)}Cl(2)(PMe(2)Ph)(3)], which react with tBuMgCl to give [Re{≡CCH=C(R)C≡CSiMe(3)}HCl(PMe(2)Ph)(3)]. Treatment of [Re{≡CCH=C(R)C≡CSiMe(3)}HCl(PMe(2)Ph)(3)] with nBu(4)NF gives [Re{≡CCH=C(R)C≡CH}HCl(PMe(2)Ph)(3)], which first isomerizes to the bicyclic complexes [Re{CH=CH-C(R)=CCH=}Cl(PMe(2)Ph)(3)], and then to the rhenabenzynes [Re{≡CCH=C(R)CH=CH}Cl(PMe(2)Ph)(3)]. The NMR spectroscopic and structural data as well as the aromatic stabilization energy (ASE) and nucleus-independent chemical-shift (NICS) values suggest that these rhenabenzynes have aromatic character.

The catalytic activity of a series of ruthenium complexes lacking cyclopentadienyl ligands has been evaluated for the cycloaddition of terminal alkynes and azides to give selectively 1,4-disubstitu...

Four C(8),C(12)-diastereoisomers, (8S,12S)-isoandrographolide (1), (8S,12R)-isoandrographolide (2), (8R,12R)-isoandrographolide (3), and (8R,12S)-isoandrographolide (4) were isolated from the aerial parts of Andrographis paniculata. The structures of the new compounds 1–3 were established on the basis of the spectroscopic data including UV, IR, NMR, HR-ESI-MS, and X-ray diffraction analysis.

A convenient method for regioselective H/D exchange between D(2)O and alcohols at the β-carbon position using the catalytic system [(p-cymene)RuCl(2)]/ethanolamine/KOH is described. This method is applicable for deuteration of both primary and secondary alcohols. The H/D exchange reactions proceed through an oxidation/modification/reduction reaction sequence. Alcohols are first temporarily oxidized to carbonyl compounds by the hydrogen transfer catalyst. The carbonyl compounds then undergo deuteration at the carbon adjacent to the carbonyl group by keto-enol tautomerization in the presence of D(2)O and a catalytic amount of base. The deuterated carbonyl compounds are then reduced to produce deuterated alcohols. In support of the reaction mechanism, a well-defined bimetallic ruthenium complex was isolated from the reaction of [{(p-cymene)RuCl(2)}(2)] with ethanolamine. The activity of this complex is similar to that of [{(p-cymene)RuCl(2)}(2)]/ethanolamine.

In our efforts to probe the reaction mechanism of the endo cycloisomerization of alkynols catalyzed by the complex [Ru(N3P)(OAc)](BPh4) (1; NP3 = N,N-bis[(pyridin-2-yl)methyl][2-(diphenylphosphino)phenyl]methanamine), the reactions of 1 with alkynes were investigated. Several complexes related to intermediates in the catalytic reactions were isolated and characterized. In the presence of DIPEA (N,N-diisopropylethanamine), complex 1 reacted with 3-butyn-1-ol to afford the Ru−oxocyclocarbene complex {Ru(N3P)[═C(CH2)3O](OAc)}(BPh4) (4). Under anhydrous conditions, the reaction of complex 1 with tert-butylacetylene afforded [Ru(N3P)(η3-tBuC≡CC═CHBut)](BPh4) (8). In the presence of water, the reaction of complex 1 with tert-butylacetylene afforded [Ru(N3P)(CO)(η1-CH2But)](BPh4) (13). All the reactions are likely to proceed through ruthenium vinylidene intermediates. These results support that ruthenium vinylidene complexes are involved as the key intermediates in the cycloisomerization of alkynols catalyzed by...

The new ruthenium complex [Ru(N(3)P)(OAc)][BPh(4)] (4), in which N(3)P is the N,P mixed tetradentate ligand N,N-bis[(pyridin-2-yl)methyl]-[2-(diphenylphosphino)phenyl]methanamine was synthesized. The complex was found to be catalytically active for the endo cycloisomerization of alkynols. The catalytic reactions can be used to synthesize five-, six-, and seven-membered endo-cyclic enol ethers in good to excellent yields. A catalytic cycle involving a vinylidene intermediate was proposed for the catalytic reactions. Treatment of complex 4 with PhC[triple bond]CH and H(2)O gave the alkyl complex [Ru(CH(2)Ph)(CO)(N(3)P)][BPh(4)] (30), which supports the assumption that the catalytic reactions involve addition of a hydroxyl group to the C=C bond of vinylidene ligands.

Whereas most conventional DNA probes are flat disklike aromatic molecules, we explored the possibility of developing quadruplex sensors with nonplanar conformations, in particular, the propeller-shaped tetraphenylethene (TPE) salts with aggregation-induced emission (AIE) characteristics. 1,1,2,2- Tetrakis(4-(2-triethylammonioethoxy)- phenyl)ethene tetrabromide (TPE-1) was found to show a specific affinity to a particular quadruplex structure formed by a human telomeric DNA strand in the presence of K + ions, as indicated by the enhanced and batho- chromically shifted emission of the AIE fluorogen. Steady-state and time- resolved spectral analyses revealed that the specific binding stems from a struc- tural matching between the AIE fluor- ogen and the DNA strand in the fold- ing process. Computational modeling suggests that the AIE molecule docks on the grooves of the quadruplex sur- face with the aid of electrostatic attrac- tion. The binding preference of TPE-1 enables it to serve as a bioprobe for direct monitoring of cation-driven con- formational transitions between the quadruplexes of various conformations, a job unachievable by the traditional G-quadruplex biosensors. Methyl thia- zolyl tetrazolium (MTT) assays reveal that TPE-1 is cytocompatible, posing no toxicity to living cells.

New catalyst systems for diyne polycyclotrimerization were developed. E-1-[2-(2,5-Diethynylphenyl)vinyl]ferrocene (1), a ferrocene-containing diyne, was polymerized by ruthenium- and rhodium-based catalysts, affording hyperbranched polyphenylenes (hb-P1) with high molecular weights (Mw up to ∼1.4 × 105) in high yields (up to 100%). Effects of reaction conditions on the polymerization process were investigated, and structures of the resultant polymers were characterized by spectroscopic methods. The polymers were soluble, thermally stable, and redox active. Complexation with cobalt carbonyls further metalized the polymers. Both the polymers and their cobalt complexes showed high refractive indices (RI up to ∼1.81) at 300−1700 nm, large Abbe numbers (νD′ up to ∼681), and low optical dispersions (D′ down to ∼0.0015) in the telecommunication wavelength region. Pyrolyses of the polymers and their complexes furnished magnetic ceramics with high magnetizabilities (Ms up to ∼83 emu/g).

Step by step: By attaching anionic building blocks of variable bulk to a cationic metal-organic framework, stepwise channel-size adjustment of the resulting porous three-dimensional host framework is achieved (see picture). This method is a new and viable approach for materials with predesigned nanopores for application in molecular recognition and selective guest inclusion.Through the introduction of perfluorocarboxylates as counteranions that line the inner surface of each channel in a host cationic metal-organic open framework, stepwise channel-size control has been realized, resulting in wide guest compatibility for [{Ag(L)(CF(3)CO(2))}(6)6 G](infinity) (1 supersetG; G=guest, L=ligand), selective guest recognition for [{Ag(L)(C(2)F(5)CO(2))}(6)4 G'](infinity) (2 supersetG'), and a lack of inclusion behavior for [{Ag(L)(C(3)F(7)CO(2))}(6)](infinity) (3; G and G' represent the same or different guest molecules). The cationic frameworks in 1-3 are constructed from the linkage of hexameric inorganic-organic hybrid macrocycles through multiple argentophilic interaction plus pi-pi interactions between pyridyl rings and carbonyl-carbonyl interactions, to which corresponding counteranions are attached. With different anions as intrachannel arms, similar frameworks in complexes 1 supersetG, 2 supersetG', and 3 exhibit percentages of guest-accessible voids of approximately 30-35, 25, and 18 % for 1-3, respectively. The highly flexible framework 1 in 1 supersetG contains stretchable channels with up to 21.7 % effective-volume change of the solvent-accessible void for inclusion of various guest species in the series of solvates 1 a-m. The pair of complexes 1 supersetG and [Ag(L)(CF(3)CO(2))](infinity) (4), and likewise the pair 2 supersetG' and [Ag(L)(C(2)F(5)CO(2))](infinity) (5), are interconvertible through distinct controllable processes.

The first catalytic asymmetric desymmetrization of azetidines is disclosed. Despite the low propensity of azetidine ring opening and challenging stereocontrol, smooth intermolecular reactions were realized with excellent efficiency and enantioselectivity. These were enabled by the suitable combination of catalyst, nucleophile, protective group, and reaction conditions. The highly enantioenriched densely functionalized products are versatile precursors to other useful chiral molecules. Mechanistic studies, including DFT calculations, revealed that only one catalyst molecule is involved in the key transition state, though both reactants can be activated. Also, the Curtin–Hammett principle dictates the reaction proceeds via amide nitrogen activation.

The first catalytic asymmetric desymmetrization of azetidines is disclosed. Despite the low propensity of azetidine ring opening and challenging stereocontrol, smooth intermolecular reactions were realized with excellent efficiency and enantioselectivity. These were enabled by the suitable combination of catalyst, nucleophile, protective group, and reaction conditions. The highly enantioenriched densely functionalized products are versatile precursors to other useful chiral molecules. Mechanistic studies, including DFT calculations, revealed that only one catalyst molecule is involved in the key transition state, though both reactants can be activated. Also, the Curtin–Hammett principle dictates the reaction proceeds via amide nitrogen activation.

Treatment of titanyl sulfate in about 60 mM sulfuric acid with NaL(OEt) (L(OEt) (-)=[(eta(5)-C(5)H(5))Co{P(O)(OEt)(2)}(3)](-)) afforded the mu-sulfato complex [(L(OEt)Ti)(2)(mu-O)(2)(mu-SO(4))] (2). In more concentrated sulfuric acid (>1 M), the same reaction yielded the di-mu-sulfato complex [(L(OEt)Ti)(2)(mu-O)(mu-SO(4))(2)] (3). Reaction of 2 with HOTf (OTf=triflate, CF(3)SO(3)) gave the tris(triflato) complex [L(OEt)Ti(OTf)(3)] (4), whereas treatment of 2 with Ag(OTf) in CH(2)Cl(2) afforded the sulfato-capped trinuclear complex [{(L(OEt))(3)Ti(3)(mu-O)(3)}(mu(3)-SO(4)){Ag(OTf)}][OTf] (5), in which the Ag(OTf) moiety binds to a mu-oxo group in the Ti(3)(mu-O)(3) core. Reaction of 2 in H(2)O with Ba(NO(3))(2) afforded the tetranuclear complex (L(OEt))(4)Ti(4)(mu-O)(6) (6). Treatment of 2 with [{Rh(cod)Cl}(2)] (cod=1,5-cyclooctadiene), [Re(CO)(5)Cl], and [Ru(tBu(2)bpy)(PPh(3))(2)Cl(2)] (tBu(2)bpy=4,4'-di-tert-butyl-2,2'-dipyridyl) in the presence of Ag(OTf) afforded the heterometallic complexes [(L(OEt))(2)Ti(2)(O)(2)(SO(4)){Rh(cod)}(2)][OTf](2) (7), [(L(OEt))(2)Ti(O)(2)(SO(4)){Re(CO)(3)}][OTf] (8), and [{(L(OEt))(2)Ti(2)(mu-O)}(mu(3)-SO(4))(mu-O)(2){Ru(PPh(3))(tBu(2)bpy)}][OTf](2) (9), respectively. Complex 9 is paramagnetic with a measured magnetic moment of about 2.4 mu(B). Treatment of zirconyl nitrate with NaL(OEt) in 3.5 M sulfuric acid afforded [(L(OEt))(2)Zr(NO(3))][L(OEt)Zr(SO(4))(NO(3))] (10). Reaction of ZrCl(4) in 1.8 M sulfuric acid with NaL(OEt) in the presence Na(2)SO(4) gave the mu-sulfato-bridged complex [L(OEt)Zr(SO(4))(H(2)O)](2)(mu-SO(4)) (11). Treatment of 11 with triflic acid afforded [(L(OEt))(2)Zr][OTf](2) (12), whereas reaction of 11 with Ag(OTf) afforded a mixture of 12 and trinuclear [{L(OEt)Zr(SO(4))(H(2)O)}(3)(mu(3)-SO(4))][OTf] (13). The Zr(IV) triflato complex [L(OEt)Zr(OTf)(3)] (14) was prepared by reaction of L(OEt)ZrF(3) with Me(3)SiOTf. Complexes 4 and 14 can catalyze the Diels-Alder reaction of 1,3-cyclohexadiene with acrolein in good selectivity. Complexes 2-5, 9-11, and 13 have been characterized by X-ray crystallography.

(4-Biphenylyl)phenyldibenzofulvene is weakly luminescent in the amorphous phase but becomes highly emissive upon crystallization; this unusual crystallization-induced emission enhancement effect allows its emission to be repeatedly switched between dark and bright states by fuming-heating and heating-cooling processes.