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1,1-Bis(2'-thienyl)-2,3,4,5-tetraphenylsilole (1) was prepared and characterized crystallographically. Silole 1 exhibited aggregation-induced emission (AIE) behavior like other 2,3,4,5-tetraphenylsiloles. Unexpectedly, aggregates formed in water/acetone (6:4 by volume) mixture emitted a blue light that peaked at 474 nm, while aggregates formed in the mixtures with higher water fractions emitted green light that peaked at 500 nm. Transmission electron microscopy demonstrated that the aggregates formed in the mixture with water fraction of 60% were single crystals, while aggregates that formed in the mixture with water fraction of 90% were irregular and poorly ordered particles. The unusual PL spectral reliance on aggregation order was further confirmed by PL emissions of macroscopic crystal powders and amorphous powders of the silole in the dry state. PL spectral blue shifting was observed upon aging of the poorly ordered aggregates formed in mixtures with water fractions of 70-90%, and they finally exhibited the same blue emission as the crystalline aggregates. The as-deposited thin solid film was amorphous and it could be transformed to a transparent crystalline film upon treatment in the vapor of an ethanol/water (1:1 by volume) mixture, along with PL spectral blue shifting due to changing of aggregation order. It was also found that the crystalline film showed a blue-shifted absorption spectrum relative to the amorphous film and the shift of the absorption edge of the spectra could match that of corresponding PL spectra. The FT-IR spectrum of crystal powders of 1 displayed more vibration modes compared with that of amorphous powders, suggesting the existence of different pi-overlaps or different molecular conformations. The crystals of 1-methyl-1,2,3,4,5-pentaphenylsilole and hexaphenylsilole also showed blue-shifted PL emissions of their amorphous solids, with a comparable PL spectral shift of 1. Developing of a silole solution on a TLC plate readily brought about an amorphous thin layer. Our results suggest that crystalline films of AIE-active siloles are potential emissive layers for efficient blue OLEDs with stable color and long lifetime.

Treatment of 2,4,6-tris(4-bromophenyl)-1,3,5-triazine (2,4,6-(4-BrC6H4)3-1,3,5-C3N3)with HC⋮CSiMe3in the presence of Pd(PPh3)4/CuI and NEt3 produces 2,4,6-[4-(Me3SiC⋮C)C6H4]3-1,3,5-C3N3, which reacts with Bu4NF to yield 2,4,6-[4-(HC⋮C)C6H4]3-1,3,5-C3N3. Reaction of 2,4,6-[4-(HC⋮C)C6H4]3-1,3,5-C3N3 with AuCl(PPh3) in the presence of NEt3 produces the gold acetylide complex 2,4,6-[4-((PPh3)AuC⋮C)C6H4]3-1,3,5-C3N3. Treatment of 2,4,6-[4-(HC⋮C)C6H4]3-1,3,5-C3N3 with cis-RuCl2(dppe)2/NaPF6 followed by NEt3 gives 2,4,6-[4-(Cl(dppe)2RuC⋮C)C6H4]3-1,3,5-C3N3, which reacts with p-HC⋮CC6H4R (R = OCH3, NO2) to give 2,4,6-[4-((4-RC6H4C⋮C)(dppe)2RuC⋮C)C6H4]3-1,3,5-C3N3. The electrochemical and photophysical properties of the new complexes have been investigated.

Three new diterpenoids, yuexiandajisu D (1), E (2) and F were isolated from the roots of Euphorbia ebracteolata, along with eight known diterpenoids, jolkinolide B (4), jolkinolide A, ent-11alpha-hydroxyabieta-8(14),13(15)-dien-16,12alpha-olide (6), ent-(13S)-hydroxyatis-16-ene-3,14-dione, ent-3beta,(13S)-dihydroxyatis-16-en-14-one, ent-3-oxokaurane-16alpha,17-diol, ent-16alpha,17-dihydroxyatisan-3-one and ent-atisane-3beta,16alpha,17-triol. The structures of all compounds were deduced using spectroscopic methods and confirmed for 1 and 2 by single-crystal X-ray diffraction. A biogenetic pathway for the formation of 1 and 2 is proposed briefly. Cytotoxic activities were evaluated against ANA-1, B 16 and Jurkat tumor cells. Jolkinolide B (4) displayed modest activity on ANA-1, B 16 and Jurkat tumor cells with IC50 values 4.46 x 10(-2), 4.48 x 10(-2), 6.47 x 10(-2) microM, and ent-11alpha-hydroxyabieta-8(14),13(15)-dien-16,12alpha-olide (6) showed significant activity against ANA-1 and Jurkat cells with IC50 values 7.12 x 10(-3) and 1.79 x 10(-2) microM. Compound 1 was found to be slightly active against ANA-1 cells with an IC50 value 2.88 x 10(-1)microM. Structure-activity relationships of isolated compounds are also discussed.

Treatment of Ni(HP1) (H3P1 = meso-5-[4′-(2″-pyridyl)phenyl]-10,15,20-triphenyporphyrin) with K2[PdCl4] in EtOH afforded [Pd{Ni(P1)}]2(μ-Cl)2 that reacted with NaS2CNEt2 to give Pd(S2CNEt2)[Ni(P1)]. Reaction of Ni(HP1) with [Ir(H)2(PPh3)2(Me2CO)2][BF4] afforded Ir(H)Cl(PPh3)2[Ni(P1)]. The crystal structures of Pd(S2CNEt2)[Ni(P1)] and Ir(H)(Cl)(PPh3)2[Ni(P1)] have been determined.

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.

Treatment of Na[P(O)(S-BINOL)] (S-BINOL = (S)-(−)-bi-2-naphthol) with [CpCo(CO)I2] afforded the chiral C3-symmetric oxygen tripodal ligand Na[Co{P(O)(S-BINOL)}3] (Na(1)). Recrystallization of Na(1) from acetone/toluene yielded Na(1)(C6H12O2)2 (C6H12O2 = diacetone alcohol), which has been characterized by X-ray diffraction. The solid-state structure of Na(1)(C6H12O2)2 features a six-coordinated Na with one η2 and one η1 diacetone alcohol ligand. Treatment of Na(1) with [(η6-p-cymene)RuCl2]2, [Ru(CO)Cl(CHCHPh)(PPh3)3], and [Pr(OTf)3] (OTf = triflate) afforded [(η6-p-cymene)Ru(1)][PF6] (3), [Ru(1)(CO)(CHCHPh)(PPh3)] (4), and [Pr(1)2(OTf)] (5), respectively. Treatment of Na(1) with [Cu(MeCN)4][BF4] in the presence of PhC⋮CH and Me3SiC⋮CSiMe3 afforded [Cu(1)(η2-PhC⋮CH)] (6) and [Cu(1)(η2-Me3SiC⋮CSiMe3)] (7), respectively, which have been characterized by X-ray diffraction. In both 6 and 7, the Cu atom exhibits a distorted 2 + 1 tripod ligand coordination with one Cu−O bond significantly longer than the other t...

Luminogens with aggregation-induced emission characteristics (AIEgens) are intriguing due to its rapid expansion in various high-tech applications. However, there is still in high demand on the development of novel AIEgens with easy preparation and functionalization, stable structures, tunable emissions, and high quantum efficiency. In this contribution, three AIEgens based on diphenyl isoquinolinium (IQ) derivatives are reported. They can be facilely synthesized and possess high structural stability, favorable visible light excitation, large Stokes shifts, high quantum yields, tunable colors, and sufficient two-photon absorption of near-infrared light. Importantly, they exhibit multifunctionalities. They exhibit mechanochromic property, making them capable to be applied for rewritable papers. They can also be applied in mitochondrial imaging with high specificity, cell permeability, brightness, biocompatibility, and photostability. They are promising for the applications in evaluation of mitochondrial membrane potential and image-guided cancer cell ablation. Last, they are able to stain bacteria in a wash-free manner. All these intriguing results suggest such readily accessible and multifunctional diphenyl IQ-based AIEgens provide a new platform for construction of advanced materials for practical applications.

Red/near-infrared (NIR) fluorescent molecules with aggregation-induced emission (AIE) characteristics are of great interest in bioimaging and therapeutic applications. However, their complicated synthetic approaches remain the major barrier to implementing these applications. Herein, a one-pot synthetic strategy to prepare a series of red/NIR-emissive AIE luminogens (AIEgens) by fine-tuning their molecular structures and substituents is reported. The obtained AIEgens possess simple structures, good solubilities, large Stokes shifts, and bright emissions, which enable their applications toward in vitro and in vivo imaging without any pre-encapsulation or -modification steps. Excellent targeting specificities to lipid droplets (LDs), remarkable photostabilities, high brightness, and low working concentrations in cell imaging application make them remarkably impressive and superior to commercially available LD-specific dyes. Interestingly, these AIEgens can efficiently generate reactive oxygen species upon visible light irradiation, endowing their effective application for photodynamic ablation of cancer cells. This study, thus, not only demonstrates a facile synthesis of red/NIR AIEgens for dual applications in simultaneous imaging and therapy, but also offers an ideal architecture for the construction of AIEgens with long emission wavelengths.

In this contribution, we finely tuned the singlet-triplet energy gap (ΔEST) of AIE-active materials to modulate their fluorescence, phosphorescence and delay fluorescence via rational molecular design and investigated the possible ways to harvest their triplet energy in OLEDs. Noteworthily, two molecules o-TPA-3TPE-o-PhCN and o-TPA-3TPE-p-PhCN with larger ΔEST values (0.59 eV and 0.45 eV, respectively) emitted efficient long-lived low temperature phosphorescence in their glassy solutions and exhibited efficient crystallization-induced room temperature phosphorescence (RTP). Meanwhile, it was the first time to observe a novel crystallization-induced delay fluorescence phenomenon in another AIE-active molecule p-TPA-3TPE-p-PhCN owing to its very small ΔEST value (0.21 eV). It was also found that molecules with various ΔEST values showed significantly different temperature sensitivity. Non-doped electroluminescent (EL) devices using these molecules as light-emitting layers were fabricated, exhibiting external quantum efficiencies (EQE) higher than theoretical values of purely singlet emitter type devices. Particularly, p-TPA-3TPE-p-PhCN showed outstanding device performances with high luminance and efficiencies up to 36,900 cd m(-2), 11.2 lm W(-1), 12.8 cd A(-1) and 4.37%, respectively, considering that its solid-state quantum yield was only 42%. All the above observations suggested that tuning the ΔEST values of AIE materials is a powerful methodology to generate many more interesting and meaningful optoelectronic properties.

Herein, a new series of siloles that were 2,5-substituted with planar fluorescent chromophores (PFCs), including fluorene, fluoranthene, naphthalene, pyrene, and anthracene, were synthesized and characterized. These compounds showed weak emission in the solution state, owing to active intramolecular rotation (IMR), but the synergistic effect from electronic coupling between the PFC and the silole ring compensated for the emission quenching by the IMR process to some extent, thereby affording higher emission efficiencies than those of 2,3,4,5-tetraphenylsiloles in solution. These new siloles showed enhanced emission efficiencies in the aggregated state. The electroluminescence (EL) color and efficiency of new siloles were sensitive towards the PFC. Siloles containing naphthalene moieties showed green EL emission, whilst those containing anthracene moieties showed orange EL emission. The siloles containing pyrene moieties exhibited yellow EL emission at 546 nm, with a peak luminance of 49000 cd cm(-2) and a high current efficiency of 9.1 cd A(-1).

Hydrothermal synthesis using V2O5, Mn(OAc)2, 1,3-diaminopropane (pn) and oxalic acid at pH 7 and 110°C results in the formation of a hybrid organic–ceramic solid [H2pn][Mn2(C2O4)(V4O12)] 1, with an anionic open-framework composed of Mn2+ ions, oxalate and cyclotetravanadate ions. 7 A cavities house the organic [H2pn] countercations. The crystal structure shows 1 is monoclinic, P21/m, a=8.680(2), b=11.728(2), c=9.639(2) A, β=114.56(1)°, V=892.5(3) A3. An isostructural material 2 [H2bn][Mn2(C2O4)(V4O12)] can be formed using 1,4-diaminobutane (bn).

Molten boric acid ‘flux’ synthesis has been used to prepare pure [Cu(en)2][B7O13H3]n 1 in a 70% yield by heating Cu(NO3)2·3H2O, en and H3BO3 in a 1:6:13 ratio at 180°C for 3 days. Compound 1 is triclinic P-1, a=7.846(1), b=8.285(1), c=15.477(1) A, α=99.14(1), β=96.05(1), γ=117.02(1)°, V=866.7 A3. The coppers are square planar with two trans (en) chelates (Cu–N=2.00–2.03 A). They have only weak axial interactions to hydroxyborates (Cu–O=2.50–2.57 A). The [B7O13H3]n polymer component exists as anionic 2-D sheets, that associate through O–H–O hydrogen bond pairs to create an open 3-D shell about the structure-directing [Cu(en)2] counter-ions.

Synthesis of [enH2][Mn3(V2O7)2(H2O)2] 1, the first of a new class of organically derivatized mixed metal oxides, is achieved at pH 8 and 140°C by hydrothermal reaction of [Mn3O(OAc)6(py)3][BF4], V2O5, NH2CH2CH2NH2 (en) and H3BO3 in a 0.67: 1: 6: 10 ratio. Crystals of 1 are triclinic P-1, a=5.743(1) A, b=7.931(1) A, c=9.313(1) A, α=68.54(1), β=85.78(1), γ=84.50(1)°, V=392.62(9) A3. The X-ray structure refined to R=0.025. Compound 1 has an anionic open 3-D framework based on linear tri-manganese units of edge shared [Mn(II)O6] octahedra connected through divanadate [V2O7] groups. The organic counterions are located in 1-D tunnels generated from six-membered [Mn2V4] rings. The temperature dependent magnetic susceptibility of 1 indicates a paramagnetic to anti-ferromagnetic transition with a Neel temperature of 10 K.

A fluorinated mixed-metal phosphate containing indium and cobalt in 1:1 ratio, [enH 2 ][CoIn(PO 4 ) 2 H(OH 2 ) 2 F 2 ], 1, has been synthesized by hydrothermal methods from a gel-composition of 1.0 Co(OAc) 2 : 1.0 In(OAc) 3 : 2.0 H 3 PO 4 : 2.0 en: 2.0 HF: 240 H 2 O. Large pale pink-purple single crystals (200 μm) were formed in 70% yield based on cobalt, with only minor amorphous impurity phases. Compound 1 is triclinic, space group P 1 , a =5.217(1), b =7.596(2), c =8.904(2) A, α =109.11(1), β =97.46(1), γ =109.95(1)°, V =301.6(1) A 3 . The magnetic moment is 5.02 BM, indicating a d 7 high-spin Co 2+ center. Fluoride is crucial to formation of the mixed-metal phase since the In and Co metals are connected to each other by bent F − bridges, as well as hydrogen phosphate groups, which connect the (Co–F–In) chains into a 2-D sheet structure.

(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.

Hydrothermal reaction of Zr(OPr) 4 with H 3 PO 4 in the presence of ethylene diamine and HF yields three crystalline phases; the 1-D [enH 2 ][Zr(HPO 4 ) 3 ], 1, which can grow as needles over 1 mm in length, the 2-D [enH 2 ] 0.5 [Zr(PO 4 )(HPO 4 )], 2, which is found as thin plates, and the previously reported fluorinated 3-D open-framework compound [enH 2 ] 0.5 [Zr 2 (PO 4 ) 2 (HPO 4 )F]. H 2 O, 3. The 1-D phase is the first of its type, with each Zr linked to neighboring metal atoms in the chain by three bridging phosphate groups via Zr–O–P–O–Zr linkages. Its crystals are monoclinic, space group C 2/ c , a =8.996(3), b =15.373(5), c =9.582(4) A, β =102.97(2)°, V =1287(1) A 3 . Compound 2 is orthorhombic, space group Pnnm , a =24.087(4), b =5.381(1), c =6.660(1) A, V =863.0(4) A 3 . It is related to the ‘double layer’ sheet compound γ -ZrP and its ion exchanged analogues.

η(5)-η(1) ring slippage of [OsCp2] (Cp = η(5)-C5H5) and [Ru(η(5)-ind)2] (ind = indenyl) resulting from reaction with the ruthenium(VI) nitride [Ru(L(OEt))(N)Cl2] (1; L(OEt)(-) = [CoCp{P(O)(OEt)2}3](-)) is reported. The treatment of [OsCp2] or [Ru(η(5)-ind)2] with 1 resulted in η(5)-η(1) ring slippage of the cycloolefin ligands and formation of the trinuclear nitrido complexes [Cp(η(1)-C5H5)Os(NRuL(OEt)Cl2)2] (2) or [(η(5)-ind)(η(1)-ind)Ru(NRuL(OEt)Cl2)2] (3). No reactions were found between [OsCp2] and amines, such as pyridine and 2,2'-bipyridyl, or other metal nitrides, such as [Os(L(OEt))(N)Cl2], indicating that the electrophilic property of 1 is essential for ring slippage. The crystal structures of 2 and 3 have been determined. The short Os-N distances in 2 [1.833(5) and 1.817(5) A] and the (ind)Ru-N distances in 3 [1.827(5) and 1.852(5) A] are indicative of multiple bond character, consistent with density functional theory (DFT) calculations. Therefore, 2 and 3 may be described by two resonance forms: Ru(VI)-M(II)-Ru(VI) and Ru(IV)-M(VI)-Ru(IV) (M = Os, Ru). Also, DFT calculations indicate that for the reaction of 1 with [OsCp2] or [Ru(η(5)-ind)2], η(5)-η(1) ring slippage is energetically more favorable than the η(5)-η(3) counterpart. The driving force for η(5)-η(1) ring slippage is believed to be the formation of the strong M-N (M = Os, Ru) (multiple) bonds. By contrast, the same reaction with acetonitrile is energetically uphill, and thus no ring slippage occurs.

An organocatalytic diastereoselective synthesis of 3-amino-1-indanols (III) and (V), a privileged skeleton of significant importance in organic synthesis and medicinal chemistry, is described.

2,3,4,5-Tetraarylsiloles are a class of important luminogenic materials with efficient solid-state emission and excellent electron-transport capacity. However, those exhibiting outstanding electroluminescence properties are still rare. In this work, bulky 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, and 9,9'-spirobifluorenyl substituents were introduced into the 2,5-positions of silole rings. The resulting 2,5-difluorenyl-substituted siloles are thermally stable and have low-lying LUMO energy levels. Crystallographic analysis revealed that intramolecular π-π interactions are prone to form between 9,9'-spirobifluorene units and phenyl rings at the 3,4-positions of the silole ring. In the solution state, these new siloles show weak blue and green emission bands, arising from the fluorenyl groups and silole rings with a certain extension of π conjugation, respectively. With increasing substituent volume, intramolecular rotation is decreased, and thus the emissions of the present siloles gradually improved and they showed higher fluorescence quantum yields (Φ(F) =2.5-5.4%) than 2,3,4,5-tetraphenylsiloles. They are highly emissive in solid films, with dominant green to yellow emissions and good solid-state Φ(F) values (75-88%). Efficient organic light-emitting diodes were fabricated by adopting them as host emitters and gave high luminance, current efficiency, and power efficiency of up to 44,100 cd m(-2), 18.3 cd A(-1), and 15.7 lm W(-1), respectively. Notably, a maximum external quantum efficiency of 5.5% was achieved in an optimized device.

In this paper, a simple strategy to change the emission behaviour of luminogenic materials was developed. Tetraphenylethene (TPE)-functionalised benzothiazolium salts with different counteranions (TPEBe-X; X=I(-), ClO(4)(-) and PF(6)(-)) were designed and synthesised. All the luminogens show weak red emission in the solution state that originates from intramolecular charge transfer from TPE to the benzothiazolium unit. Whereas aggregate formation enhances the light emission of TPEBe-ClO(4) and TPEBe-PF(6), that of TPEBe-I is quenched, thus demonstrating the phenomena of aggregation-induced emission and aggregation-caused quenching. TPEBe-I works as a light-up fluorescent sensor for Hg(2+) in aqueous solution with high sensitivity and specificity owing to the elimination of the emission quenching effect of the iodide ion by the formation of HgI(2) as well as the induction in aggregate formation by the complexation of Hg(2+) with the S atom of the benzothiazolium unit of TPEBe-I. A solid film of TPEBe-I was prepared that can monitor the level of Hg(2+) in aqueous solution with a detection limit of 1 μM.

Heterometallic cerium(IV) perrhenate, permanganate, and molybdate complexes containing the imidodiphosphinate ligand [N(i-Pr2PO)2](-) have been synthesized, and their reactivity was investigated. Treatment of Ce[N(i-Pr2PO)2]3Cl (1) with AgMO4 (M = Re, Mn) afforded Ce[N(i-Pr2PO)2]3(ReO4) (2) or Ce2[N(i-Pr2PO)2]6(MnO4)2 (3). In the solid state, 3 is composed of a [Ce2{N(i-Pr2PO)2}6(MnO4)](+) moiety featuring a weak Ce-OMn interaction [Ce-OMn distance = 2.528(8) Å] and a noncoordinating MnO4(-) counteranion. While 3 is stable in the solid state and acetonitrile solution, it decomposes readily in other organic solvents, such as CH2Cl2. 3 can oxidize ethylbenzene to acetophenone at room temperature. Treatment of 1 with AgBF4, followed by reaction with [n-Bu4N]2[MoO4], afforded [Ce{N(i-Pr2PO)2}3]2(μ-MoO4) (4). Reaction of trans-Ce[N(i-Pr2PO)2]2(NO3)2 (5), which was prepared from (NH4)2Ce(NO3)6 and K[N(i-Pr2PO)2], with 2 equiv of [n-Bu4N][Cp*MoO3] yielded trans-Ce[N(i-Pr2PO)2]2(Cp*MoO3)2 (6). 4 can catalyze the oxidation of methyl phenyl sulfide with tert-butyl hydroperoxide with high selectivity. The crystal structures of complexes 3-6 have been determined.

In the title compound, C8H4N2O4F6S, N—H⋯N hydrogen bonds [N⋯N = 2.857 (3) and 2.862 (3) A] form a dimer from the two independent mol­ecules in the asymmetric unit and dictate the conformation of the mol­ecule. The dimers are connected by weak intermolecular C—H⋯O and F⋯F interactions to form a two-dimensional supramolecular architecture.

An efficient organocatalyzed strategy for the synthesis of 3-amino-1-indanols has been developed. This method is complementary to the conventional Friedel–Crafts strategy. It is also applicable to the synthesis of enantioenriched 3-amino-1-indanols.

synthesis and characterization of the new bluish-green emitter (I) with aggregation-induced emission activity and excellent electron-transport properties

2,5-Bis(triphenylsilylethynyl)-3,4-diphenylsiloles with different 1,1-substituents [XYSi(CPh)(2) (C-C≡C-SiPh(3))(2)] (Ph=phenyl) were synthesized in high yields by the Sonogashira coupling of 2,5-dibromo-3,4-diphenylsiloles with triphenylsilylacetylene, and two of these were characterized crystallographically. Crystal structures and theoretical calculations showed that the new silole molecules had higher conjugation than 2,5-diarylsiloles. They possessed low HOMO and LUMO energy levels due to the electron-withdrawing effect of the triphenylsilylethynyl groups. Cyclic voltammetry analysis revealed low electron affinities, which were comparable to those of perfluoroarylsiloles. B3LYP/6-31* calculations demonstrated that the new siloles possessed large reorganization energies for electron and hole transfers and high electron mobilities. A mobility of up to 1.2×10(-5) cm(2) V(-1) s(-1) was obtained by the transient electroluminescence method, which was about fivefold higher than that of tris(8-hydroxyquinolinato)aluminum, a widely used electron-transport material, under the same conditions. All of the silole molecules possessed high thermal stability. Although, their solutions were weakly emissive, their nanoparticle suspensions and thin films emitted intense blue-green light upon photoexcitation, demonstrating a novel feature of aggregation-induced emission (AIE). Polarized emissions were observed in the silole crystals. The addition of solvents, which did not dissolve the silole molecules, into silole-containing solutions caused self-assembly of the molecules, which produced macroscopic fibrils with strong light emissions.

Five-, six-, and seven-membered endocyclic enol ethers are prepared in good to excellent yield by the title reaction.

Synthesis of [enH2][Mn3(V2O7)2(H2O)2] 1, the first of a new class of organically derivatized mixed metal oxides, is achieved at pH 8 and 140°C by hydrothermal reaction of [Mn3O(OAc)6(py)3][BF4], V2O5, NH2CH2CH2NH2 (en) and H3BO3 in a 0.67: 1: 6: 10 ratio. Crystals of 1 are triclinic P-1, a=5.743(1) A, b=7.931(1) A, c=9.313(1) A, α=68.54(1), β=85.78(1), γ=84.50(1)°, V=392.62(9) A3. The X-ray structure refined to R=0.025. Compound 1 has an anionic open 3-D framework based on linear tri-manganese units of edge shared [Mn(II)O6] octahedra connected through divanadate [V2O7] groups. The organic counterions are located in 1-D tunnels generated from six-membered [Mn2V4] rings. The temperature dependent magnetic susceptibility of 1 indicates a paramagnetic to anti-ferromagnetic transition with a Neel temperature of 10 K.

[Ba3Cl2][Sn3O4(OH)8] (1), is formed through hydrothermal synthesis in the BaCl2/SnCl4 system. 1 is orthorhombic, Pnma, a=7.836(2), b=18.350(4), c=10.258(2) A, V=1475 A3 and composed of alternating layers of covalent stannate and ionic barium chloride components. The ‘covalent’ layers consist of hydroxy stannate trimers [Sn3O4(OH)8], connected through μ3-O to other units forming puckered 2-D sheets. These sheets are then intercalated by the barium and chloride ions, which have a complex set of ionic contacts.

Chemical investigation of rhizomes of Homalomena occulta (Lours) resulted in isolation and identification of two sesquiterpenoids (6,7), and one daucane ester 8, together with five known sesquiterpenoids, oplodiol, oplopanone, homalomenol C, bullatantriol, and 1β,4β,7α-trihydroxyeudesmane. Their structures were elucidated using 1D and 2D NMR spectroscopic and X-ray analyses. The chloroform extract of this plant and compounds 1–7 were tested in vitro for their activities in stimulating osteoblast (OB) proliferation, differentiation and mineralization. Compounds 1–4 had a stimulative effect on significantly proliferation and differentiation of culture osteoblasts, while the chloroform extract and 1 significantly stimulated mineralization of cultured osteoblasts in vitro.

Four new cadinane sesquiterpenes (1- 4), including a dimeric cadinane derivative (2) and a peroxide cadinane analogue (3), have been isolated from the leaves of Eupatorium adenophorum. Their structures including absolute configurations were determined on the basis of spectroscopic data interpretation and single-crystal X-ray crystallography. Compound 4 showed in vitro cytotoxicity against the HCT-8, Bel-7402, and A2780 cancer cell lines.

Interaction of [Ce(L(OEt))(2)(NO(3))(2)] (L(OEt)(-) = [Co(eta(5)-C(5)H(5)){P(O)(OEt)(2)}(3)](-)) with (NH(4))(6)[Mo(7)O(24)] in water affords the cerium(iv)-containing oxomolybdenum cluster [H(4)(CeL(OEt))(6)Mo(9)O(38)], which exhibits a unique Ce(6)Mo(9)O(38) core structure.

Three functionalized derivatives of tetraphenylethylene (TPE), namely, 1,2-bis(4-methoxyphenyl)-1,2-diphenylethene (1), 1,2-bis(4-hydroxyphenyl)-1,2-diphenylethene (2), and 1,2-bis[4-(3-sulfonatopropoxyl)phenyl]-1,2-diphenylethene sodium salt (3), were synthesized and their fluorescence properties were investigated. All the TPE molecules are nonluminescent in the solution state but are induced to emit efficiently by aggregate formation. This novel process of aggregation-induced emission (AIE) is rationalized to be caused by the restriction of intramolecular rotations of the dye molecules in the aggregate state. The possibility of utilizing the AIE effect for protein detection and quantification is explored using bovine serum albumin (BSA) as a model protein, with salt 3 being found to perform as a stable, sensitive, and selective bioprobe.

A Dy@C82 derivative bearing a single phosphorus substituent has been obtained in 90% yield by the regio- and chemoselective zwitterion reaction of Dy@C82 with dimethyl acetylenedicarboxylate and triphenylphosphine. The structure of the product is confirmed by MS, UV−vis−NIR spectroscopy, and X-ray crystallography.

Treatment of the osmabenzyne Os([triple bond]CC(SiMe(3))=C(Me)C(SiMe(3))=CH)Cl(2)(PPh(3))(2) (1) with 2,2'-bipyridine (bipy) and thallium triflate (TlOTf) produces the thermally stable dicationic osmabenzyne [Os([triple bond]CC(SiMe(3))=C(Me)C(SiMe(3))=CH)(bipy)(PPh(3))(2)](OTf)(2) (2). The dicationic osmabenzyne 2 reacts with ROH (R = H, Me) to give osmabenzene complexes [Os(=C(OR)CH=C(Me)C(SiMe(3))=CH)(bipy)(PPh(3))(2)]OTf, in which the metallabenzene ring deviates significantly from planarity. In contrast, reaction of the dicationic complex 2 with NaBH(4) produces a cyclopentadienyl complex, presumably through the osmabenzene intermediate [Os(=CHC(SiMe(3))=C(Me)C(SiMe(3))=CH)(bipy)(PPh(3))(2)]OTf. The higher thermal stability of [Os(=C(OR)CH=C(Me)C(SiMe(3))=CH)(bipy)(PPh(3))(2)]OTf relative to [Os(=CHC(SiMe(3))=C(Me)C(SiMe(3))=CH)(bipy)(PPh(3))(2)]OTf can be related to the stabilization effect of the OR groups on the metallacycle. A theoretical study shows that conversion of the dicationic osmabenzyne complex [Os([triple bond]CC(SiMe(3))=C(Me)C(SiMe(3))=CH)(bipy)(PPh(3))(2)](OTf)(2) to a carbene complex by reductive elimination is thermodynamically unfavorable. The theoretical study also suggests that the nonplanarity of the osmabenzenes [Os(=C(OR)CH=C(Me)C(SiMe(3))=CH)(bipy)(PPh(3))(2)]OTf is mainly due to electronic reasons.

We synthesized a group of silole regioisomers 1(x,y), whose photoluminescence varied dramatically with its regiostructure. By internally hindering the intramolecular rotation, we succeeded in creating a novel silole (1(3,4)) that is strongly luminescent in solutions and whose fluorescence quantum yield in acetone is as high as 83%. We revealed that 1(3,4) was a sensitive chemosensor capable of optically discriminating nitroaromatic regioisomers of p-, o-, and m-nitroanilines. Against general belief, crystal formation of 1(2,4) blue-shifted its emission color and boosted its emission efficiency. The light-emitting diode based on the crystal of 1(2,4) emitted a strong blue light (464 nm) in a high current efficiency (5.86 cd/A).

Nonemissive fulvenes can be induced to luminesce by aggregate formation, with the crystalline aggregates emitting bluer lights more intensely than their amorphous counterparts.

Seven new ent-rosane diterpenoids, sagittines A-G (1-7), together with one new labdane diterpene, 13-epi-manoyl oxide-19-O-alpha-l-2',5'-diacetoxyarabinofuranoside (8), were isolated from the whole plant of Sagittaria sagittifolia. The structures and relative configurations of 1-8 were characterized using spectroscopic means, chemical methods, and X-ray crystallography. Compounds 1-4 exhibited antibacterial activity against the oral pathogens Streptococcus mutans ATCC 25175 and Actinomyces naeslundiis ATCC 12104, with MIC values between 62.5 and 125 microg/mL. Compound 5 was active against only A. naeslundiis ATCC 12104, with an MIC value of 62.5 microg/mL.

L-Tartrate ions can endure hydrothermal conditions up to 160 degrees C to form the robust, enantiopure open-framework coordination polymers [Ln2(L-TAR)3(H2O)2]3H2O, 1; the addition of succinate results in formation of the related [Ln2(L-TAR)2(SUC)(H2O)2]5.5H2O, with larger channels than , whereas racemic D/L-tartrate gives the more condensed [Ln2(D/L-TAR)3(H2O)2], . TAR = [C4H4O6]2-.

Appending carbazolyl groups to a hexaphenylsilole core yielded thermally and morphologically stable carbazolylsiloles; the silole carrying two carbazolyl peripheral groups showed photovoltaic activity.

The hydrothermal synthesis of three new vanadoborate compounds with elliptical (V10B28O74H8) clusters is described. The clusters contain pairs of bimetallic Zn2 or Mn2 units.

Treatment of the allenylcarbene complex OsCl2(=CPh-CH=C=CHPh)(PPh3)2 with (PPh3)AuCCR in the presence of HNEt3Cl in CH2Cl2 produces osmabenzynes Os(CC(R)=C(CH2Ph)CH=CPh)Cl2(PPh3)2.

The development of biomimetic helical polymers is a topic of current interest. Studies of these simple unnatural systems may help us to understand complex natural systems and to explore efficient strategies for assembling molecular components into hierarchical architectures. Helical polymers with π conjugation along the main chain are of particular interest because of their high-tech applications as chiral stationary phases, optical polarizing films, asymmetric electrodes, and so forth. Polyacetylene is the best known conjugated polymer and exists in an excess of one-handed helical conformation when appropriate chiral pendants are attached.1–4 Yashima et al.5 prepared helical polyacetylenes bearing poly(γ-benzyl-L-glutamate) and poly(L-glutamic acid) moieties. Masuda et al.6 synthesized chiral copolymers with amino acid side groups and found that the helix content could be controlled through the variation of the concentrations of the chiral monomers. Attracted by the academic and practical aspects, we have also worked on the synthesis of optically active polyacetylenes with naturally occurring building blocks of amino acids, saccharides, and nucleobases.7–10 The chain helicity of the polymers can be continuously and reversibly tuned by simple external stimuli such as the solvent and pH. Amphiphilic polyacetylenes, in response to changes in their environments, spontaneously assemble into a variety of morphological structures, such as helices, vesicles, honeycomb patterns, and mollusk shapes.11–13 To enrich the research field of helical polyacetylenes, in this communication, we report the first synthesis of a chiral poly(phenylacetylene) containing dipeptide appendages, and we present its chiroptical properties.

Interaction of PdCl(2)(MeCN)(2) with 2 equiv of (S(P))-(t)BuPhP(O)H (1H) followed by treatment with Et(3)N gave [Pd((1)(2)H)](2)(micro-Cl)(2) (2). Reaction of 2 with Na[S(2)CNEt(2)] or K[N(PPh(2)S)(2)] afforded Pd[(1)(2)H](S(2)CNEt(2)) (3) or Pd[(1)(2)H)[N(PPh(2)S)(2)] (4), respectively. Treatment of 3 with V(O)(acac)(2) (acac = acetylacetonate) and CuSO(4) in the presence of Et(3)N afforded bimetallic complexes V(O)[Pd(1)(2)(S(2)CNEt(2))](2) (5) or Cu[Pd(1)(2)(S(2)CNEt(2))](2) (6), respectively. X-ray crystallography established the S(P) configuration for the phosphinous acid ligands in 3 and 6, indicating that 1H binds to Pd(II) with retention of configuration at phosphorus. The geometry around Cu in 6 is approximately square planar with the average Cu-O distance of 1.915(3) A. Treatment of 2 with HBF(4) gave the BF(2)-capped compound [Pd((1)(2)BF(2))](2)(micro-Cl)(2) (7). The solid-state structure of 7 containing a PdP(2)O(2)B metallacycle has been determined. Chloride abstraction of 7 with AgBF(4) in acetone/water afforded the aqua compound [Pd((1)(2)BF(2))(H(2)O)(2)][BF(4)] (8) that reacted with [NH(4)](2)[WS(4)] to give [Pd((1)(2)BF(2))(2)](2)[micro-WS(4)] (9). The average Pd-S and W-S distances in 9 are 2.385(3) and 2.189(3) A, respectively. Treatment of [(eta(6)-p-cymene)RuCl(2)](2) with 1H afforded the phosphinous acid adduct (eta(6)-p-cymene)RuCl(2)(1H) (10). Reduction of [CpRuCl(2)](x)() (Cp = eta(5)-C(5)Me(5)) with Zn followed by treatment with 1H resulted in the formation of the Zn(II) phosphinate complex [(CpRu(eta(6)-C(6)H(5)))(t)BuPO(2))](2)(ZnCl(2))(2) (11) that contains a Zn(2)O(4)P(2) eight-membered ring.

Treatment of OsX2(PPh3)3 (X = Cl, Br) with HCCCH(OH)CCH in THF produces OsX2(CH=C(PPh3)CH(OH)CCH)(PPh3)2, which reacts with PPh3 to give osmabenzenes [Os(CHC(PPh3)CHC(PPh3)CH)X2(PPh3)2]+.

Approaches to the formation of three new types of micro-porous materials that complement zeolites will be discussed. In each case, whether metal coordination polymers, metal-linked ceramic oxide clusters, or new hybrids containing both coordination and ceramic components, engineering of the Secondary Building Unit (SBU) is of critical importance. Successful examples of these approaches include the first thermally stable 3-D micro-porous coordination polymer with chemical functionalizability [cu3(TMA)2(H2O)3]n, as well as a 3-D micro-porous cluster based material [V12B18O60H8Cd(en)(H2O)3]n.