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Porous materials bearing stepwise-controlled pore-shape change that are capable of executing sophisticated tasks are of considerable interest due to their fascinating features. In this work, we present a (3,4,6)-connected metal–organic framework built of 1D hinge-like zig–zag chain and tritopic ligand, formulated as (H3O)2[Zn3(dmtrz)2(tipa)2]·4H2O (MAC-20, Hdmtrz = 3,5-dimethyl-1H-1,2,4-triazole, H3tipa = 5-(2H-tetrazol-5-yl)isophthalic acid). By regulating the hinge angle and hydrogen bond interaction of 1D chain and tritopic ligand precisely, we realize a unique two-step pore-shape change in MAC-20 structure, which reveals that 1D chain and tritopic ligands have a synergistic effect on the structural transformation. Furthermore, the MAC-20 structure executes the sequential adsorption of indigo blue (ID) and sudan-I (SD-I) stepwise-controlled by trimethylamine and N,N-dimethylformamide, which offers the potential to exploit the flexible MOFs for smart multi-step stimuli-responsive applications.

A simple binary synthetic approach with variable [HCOOH]/[Th(IV)] ratios and the addition of water resulted in the self-assembly of six novel thorium formate complexes with well-controlled structures ranging from 0D clusters and 2D layered networks to 3D frameworks. Specifically, small [HCOOH]/[Th(IV)] promoted the formation of the hexanuclear Th6O4(OH)4(HCOO)12 core, a secondary building unit for the construction of 3D [Th6Na(μ3-O)4(μ3-OH)4(HCOO)14]·[NH2(CH3)2]·(DMF)3(H2O)5 (Th-SINAP-1), 2D [Th6(μ3-O)4(μ3-OH)4(HCOO)12(DMF)2]·(H2O)10 (Th-SINAP-2), and 0D [Th6(μ3-O)4(μ3-OH)4(HCOO)12(H2O)6]·G (Th-SINAP-3). The large [HCOOH]/[Th(IV)] inhibited the olation/oxolation reaction, affording 3D frameworks of [Th2(HCOO)9]·[NH2(CH3)2]·(DMF)(H2O)2 (Th-SINAP-4), [Th2(HCOO)9]·[NH2(CH3)2]·(DMF)(H2O)4 (Th-SINAP-5), and [Th2(HCOO)8(H2O)(DMF)]·(H2O)3 (Th-SINAP-6) with monomeric Th(IV) cations as the metal nodes. The addition of water not only affected the hydrolysis of Th(IV) to form nucleophilic hydroxo/oxo-aquo Th species, but also influenced the overall solid-state packing via the competition between H2O, HCOO−, OH−/O2−, and DMF for coordination with Th4+ cations. This unexpected structural complexity of thorium formates opens a new avenue for the targeted design and synthesis of atypical coordination polymers, e.g. open-framework materials of actinides, for applications in diverse fields such as radionuclide adsorption.

The rare-earth-metal organic cyclo-P4 complex (LY·DMAP)2[1,2-R2- cyclo-P4] (2, L = N, N'-2,6-diisopropylphenyl-1,4-diazabutadiene, DMAP = 4- N, N'-dimethylpyridine, R = CH2C6H4NMe2-2) was synthesized by direct functionalization of P4 using the rare-earth-metal alkyl complex LYR(THF) (1) for the first time. Further investigations indicated that three selective conversions of the cyclo-P4 species have been realized by alkyl migration. Complex 2 was slowly transformed into a R2P-substituted cyclo-P3 cluster (LY·DMAP)2[ cyclo-P3PR2] (3) under heating conditions. The reaction of 2 with 1 equiv of KR gave the unsubstituted cyclo-P3 complex (LY·THF)2[ cyclo-P3]K (4) in quantitative yield, accompanied by the elimination of the organophosphorus compound PR3 (5). Treatment of 2 with HMPA afforded the structurally characterized Zintl-type P7 complex (LY·HMPA)3P7 (6). The formation of complexes 3, 4, and 6 revealed that unusual alkyl migrations in the polyphosphorus complexes occurred in these reactions, and the transformations from cyclo-P4 into cyclo-P3 also provided a new insight into the stepwise degradation of P4 using metal complexes.

We report a robust and rigid etb-type metal–organic framework, in which its pore surface is decorated with flexible ethoxyl groups. It shows unprecedentedly selective adsorption of acetone (ETN value of 0.355, kinetic diameter of 4.6 A) over methanol (ETN value of 0.762, kinetic diameter of 3.6 A) for their azeotropic mixture.

Summary A series of Cp*Rh- and Cp*Ir-based molecular Borromean rings (BRs) have been prepared with dihalogenated ligands (fluoranilic acid, chloranilic acid, and bromianilic acid) and 4,4′-bipyridylacetylene. The halogen atoms play a crucial role in forming BRs. The strength of the interaction among the rings for different BRs is not the same and can be adjusted by changes in the halogen atoms on the precursor. We took advantage of this dissimilarity in the interactions to realize selective reversible conversion between BRs and a monomeric rectangle by the use of different p -dihalobenzenes. Subsequently, a stepwise separation method for p -dichlorobenzene, p -dibromobenzene, and p -diiodobenzene at ambient temperature was developed. The BRs used in the separation are recoverable and recyclable.

The mixed mono- and dianionic β-diketiminato yttrium complex [η2-N,N-{N(2,6-iPr2C6H3)C(Me)}2CH]Y[η2-N,N-N(2,6-iPr2C6H3)C(Me)CHC(═CH2)N(C6H3-iPr2-2,6)] (1) was synthesized in almost quantitive yield by the metathesis reaction of β-diketiminato potassium with YCl3 in a 3:1 molar ratio in THF at room temperature. Complex 1 reacted with 1 equiv of KCH2Ph under the same conditions to afford a linear dianionic β-diketiminato-supported Y(III)/K(I) heterobimetallic polymer {Y[μ-η2:η1-N,N-N(2,6-iPr2C6H3)C(Me)CHC(═CH2)N(C6H3-iPr2-2,6)]2-K(THF)3}∞ (2). Moreover, 2 can be transformed into the corresponding salt-type complexes [K([2.2.2]cryptand)]+{[η2-N,N-N(2,6-iPr2C6H3)C(Me)CHC(═CH2)N(C6H3-iPr2-2,6)]2Y}− (3) and [nBn4N]+{[η2-N,N-N(2,6-iPr2C6H3)C(Me)CHC(═CH2)N(C6H3-iPr2-2,6)]2Y}− (4) in high yields by the reactions of 2 with [2,2,2]-cryptand or nBu4NCl in THF, respectively. The reaction of 3 and 4 with 2 equiv of CS2 in THF at amibent temperature gave the anionic or neutral aryl-substituted dihydropyridinethione [K([...

The rare-earth-metal organic cyclo-P

Doped nanoparticles (especially bimetal doped nanoparticles) have attracted extensive interest not only for fundamental scientific research but also for application purposes. However, their indefinite composition (structure) and broad distribution hinder an insightful understanding of the interaction between these invasive metals in bimetal doped nanoparticles. Fortunately, atom-precise bimetal doped ultrasmall nanoparticles (nanoclusters) provide opportunities to obtain such insights. However, atom-precise trimetal nanoclusters and their structures have rarely been reported. Here, we successfully dope thiolated Au25 nanoclusters with Hg and Ag successively by using a biantigalvanic reduction method. We then fully characterize the as-obtained trimetal nanoclusters using multiple techniques (including single-crystal X-ray crystallography), and we demonstrate that the mercury and silver dopings exhibit not only a synergistic but also a counteractive influence on some of the physicochemical properties of Au25.

The structural features that render gold nanoclusters intrinsically fluorescent are currently not well understood. To address this issue, highly fluorescent gold nanoclusters have to be synthesized, and their structures must be determined. We herein report the synthesis of three fluorescent Au24 (SR)20 nanoclusters (R=C2 H4 Ph, CH2 Ph, or CH2 C6 H4 (t) Bu). According to UV/Vis/NIR, differential pulse voltammetry (DPV), and X-ray absorption fine structure (XAFS) analysis, these three nanoclusters adopt similar structures that feature a bi-tetrahedral Au8 kernel protected by four tetrameric Au4 (SR)5 motifs. At least two structural features are responsible for the unusual fluorescence of the Au24 (SR)20 nanoclusters: Two pairs of interlocked Au4 (SR)5 staples reduce the vibration loss, and the interactions between the kernel and the thiolate motifs enhance electron transfer from the ligand to the kernel moiety through the Au-S bonds, thereby enhancing the fluorescence. This work provides some clarification of the structure-fluorescence relationship of such clusters.

International audience; The preferential substitution of oxo ligands over alkyl ones of rare-earth complexes is commonly considered as "impossible" due to the high oxophilicity of metal centers. Now, it has been shown that simply assembling mixed methyl/oxo rare-earth complexes to a rigid trinuclear cluster framework cannot only enhance the activity of the Ln-oxo bond, but also protect the highly reactive Ln-alkyl bond, thus providing a previously unrecognized opportunity to selectively manipulate the oxo ligand in the presence of numerous reactive functionalities. Such trimetallic cluster has proved to be a suitable platform for developing the unprecedented non-redox rare-earth-mediated oxygen atom transfer from ketones to CS2 and PhNCS. Controlled experiments and computational studies shed light on the driving force for these reactions, emphasizing the importance of the sterical accessibility and multimetallic effect of the cluster framework in promoting reversal of reactivity of rare-earth oxo complexes.

Controlling the dopant type, number, and position in doped metal nanoclusters (nanoparticles) is crucial but challenging. In the work described herein, we successfully achieved the mono-cadmium doping of Au25 nanoclusters, and revealed using X-ray crystallography in combination with theoretical calculations that one of the inner-shell gold atoms of Au25 was replaced by a Cd atom. The doping mode is distinctly different from that of mono-mercury doping, where one of the outer-shell Au atoms was replaced by a Hg atom. Au24Cd is readily transformed to Au24Hg, while the reverse (transformation from Au24Hg to Au24Cd) is forbidden under the investigated conditions.

Metal–organic frameworks with tunable functional groups like solid-solution have received considerable interest. In this paper, a crs-type structure built of [Zn3(OH)(dmtrz)3] triazolate-trinuclear and [Zn2(COO)4] paddlewheel units, linked by 3,5-dimethyl-1,2,4-triazolate (dmtrz) and isophthalate (ipa) ligands (named as MAC-4-A), has been used as a prototype framework. Four types of functional groups (B: 5-hydroxyisophthalate, C: 5-aminoisophthalate, D: 5-ethoxyisophthalate, and E: 5-acetamidoisophthalate) have been integrated into the framework, giving isostructures of MAC-4-B to E, respectively. Then, by the solid-solution framework approach, four group samples are prepared, which are MAC-4-AB-x, MAC-4-AC-x, MAC-4-AD-x, and MAC-4-AE-x (x denoted as the ratio of functional ligands in the framework, x = 0.3, 0.5, 0.7), and their CO2 and N2 adsorptions have been studied. Our results revealed that the CO2 capacity is enhanced with the increase of functional groups and then decreases, showing a maximum uptak...

Two hydrogen-bonded organic frameworks (HOFs) of the melamine (MA), MA-1-H2O and MA-2-DMF, have been crystallized in H2O and DMF (N,N-Dimethylformamide), respectively. Structurally, MA-1-H2O and MA-2-DMF are condensed and porous, respectively. The porous MA-2-DMF sustains the porous feature under the solvent exchange by acetone, dichloromethane (CH2Cl2), and toluene, while it transforms into the condensed one under methanol (MeOH) and ethanol (EtOH). Furthermore, MA-2-DMF and MA-2-Toluene can undergo reversible single crystal–single crystal transformation with retention of the porous hydrogen-bonded organic frameworks.

Two metal–organic frameworks containing a geometrically spin-frustrated trinuclear-triangular copper cluster ([Cu3O]) have been successfully isolated, which are {[Cu4.5(μ3-OH)(dmtrz)3(m-bdc)2.5(H2O)2(CH3OH)(DMF)]·DMF·5H2O}n (MAC-8) and {[Cu5(μ3-OH)(dmtrz)3(bdc)3(H2O)4]·3H2O}n (MAC-9) (Hdmtrz = 3,5-dimethyl-1H-1,2,4-triazole, H2m-bdc = 1,3-benzenedicarboxylic acid, H2bdc = 1,4-benzenedicarboxylic acid, DMF = N′,N-dimethylformamide). Magnetic and gas adsorption studies revealed the successful combination of strong antiferromagnetic properties (Jav = −106.6 and −113.7 cm–1 for [Cu3O] in MAC-8 and MAC-9, respectively) and high surface areas (1058 m2/g for MAC-8 and 1242 m2/g for MAC-9) in both of the structures. Further structural studies revealed that the high surface areas could be ascribed to the unique two-dimensional hexagonal pattern of [Cu3(O)] clusters, in which the [Cu3(O)] clusters are connected to each other in an end-end fashion via mononuclear copper ions/paddle-wheel units.

A 7-connected Zn4O unit has been theoretically predicted based on basic zinc acetate [Zn4O(CH3COO)6], which was then experimentally extended into a three-dimensional structure featuring three kinds of nanocage in a unit cell.

Inorganic functionalization of metal–organic frameworks (MOFs), such as incorporation of multiple inorganic building blocks with distinct metals into one structure and further modulation of the metal charges, endows the porous materials with significant properties toward their applications in catalysis. In this work, by an exploration of the role of 4-pyrazolecarboxylic acid (H2PyC) in the formation of trinuclear copper pyrazolate as a metalloligand in situ, four new MOFs with multiple components in order were constructed through one-pot synthesis. This metalloligand strategy provides multicomponent MOFs with new topologies (tub for FDM-4 and tap for FDM-5) and is also compatible with a second organic linker for cooperative construction of complex MOFs (1,4-benzenedicarboxylic acid for FDM-6 and 2,6-naphthalenedicarboxylic acid for FDM-7). The component multiplicity of these MOFs originates from PyC’s ability to separate Cu and Zn on the basis of their differentiated binding affinities toward pyrazolate a...

The reactions of β-diketiminatoyttrium dialkyl complex LY(CH2Ph)2(THF) (1, L = [{N(2,6-iPr2C6H3)C(Me)}2CH]−) with a series of aromatic N-heterocycles such as 2-phenylpyridine, benzothiazole, and benzoxazole were studied and displayed discrete reactivity including C–H activation, C–C coupling, ring-opening/insertion, and dearomatization. The reaction of 1 with 2-phenylpyridine in 1:2 molar ratio in THF at 30 °C for 14 days afforded a structurally characterized metal complex, LY(η2-N,C-C5H4NC6H4-2)[C5H4N(CH2Ph-4)Ph] (2), in 73% isolated yield, indicating the occurrence of phenyl ring C(sp2)–H activation and pyridine ring 1,4-addition/dearomatization. However, when this reaction was done at 5 °C for 7 days, it gave the pyridine ring 1,2-addition product LY(η2-N,C-C5H4NC6H4-2)[C5H4N(CH2Ph-2)Ph] (3) in 54% isolated yield. Further investigations revealed that complex 2 is the thermodynamic controlled product and complex 3 is the kinetically controlled product; 3 converted slowly into 2, as confirmed by 1H NMR s...

Although reversible covalent activation of molecular hydrogen (H2) by transition-metal complexes is a common reaction, H2-mediated sophisticated reversible arrangements of organometallic frameworks have not yet been described. Herein, we report unusual organometallic transformations in solution that can be accomplished by uptake or release of H2. An efficient route for synthesizing air- and moisture-stable 16-electron M2L2-type metallacycles under very mild conditions has been developed. The new organometallic metallacycles favor the binding of small ligands such as MeCN, Cl(-), CO, and pyridine. The reaction of a coordinatively unsaturated 16-electron M2L2-type macrocyclic complex featuring thione ligands with 1 atm of H2 leads to the isolation of a 18-electron M2L3-type cylinder, along with hydride species. Remarkably, the obtained mixture underwent loss of H2 in a facile manner upon heating to re-form the starting M2L2-type complex. A possible mechanism is proposed for the reversible transformations.

Vacancies are common in solid materials, but it remains a challenge to introduce them at specific locations with controlled distributions. Here we report the creation of ordered metal vacancies and linker vacancies in a cubic metal-organic framework (MOF) based on Zn(II) and pyrazolecarboxylic acid by removing a quarter of the metal ions and half of the linkers. The MOF with ordered vacancies shows increased pore size, thus allowing large dye molecules to fit in the pores. Furthermore, by filling the vacancies with new metals and new linkers, eight new single-crystalline MOFs with multicomponents in absolute order are introduced. The capability of performing stepwise elimination and addition reactions systematically in extended solids without destroying the structural integrity has generated complex MOF structures which otherwise cannot be made.

A unique six-fold interpenetrated hydrogen-bonded organic framework (HOF) has been developed, for the first time, for highly selective separation of C2H4/C2H6 at room temperature and normal pressure.

Tetranuclear half-sandwich iridium or rhodium complexes were obtained in good yields from the reactions of the binuclear half-sandwich metal precursors [Cp*2M2(μ-CA)]Cl2 (1a, M = Ir; 1b, M = Rh; CA = chloranilate) or [Cp*2M2(μ-DHNA)]Cl2 (2a, M = Ir; 2b, M = Rh; H2DHNA = 6,11-dihydroxynaphthacene-5,12-dione) with diPyNI (diPyNI = N,N-bis(4-pyridyl)-1,4,5,8-naphthalenetetracarboxydiimide) in the presence of AgOTf (OTf = CF3SO3) in CH3OH, respectively. The new metallarectangles have been characterized by elemental analysis, FT-IR, 1H NMR, electrospray mass spectrometry (ESI-MS), and UV/vis absorption spectroscopy. The interactions of these metallarectangles with aromatic molecules, especially pyrene, in solution have been studied by various NMR techniques (1D, DOSY, and ROESY) and UV–vis absorption. DOSY measurements suggest that the interactions between metallarectangle 4a and pyrene are outside of the cavity. The strong π···π interactions between pyrene and the naphthalenetetracarboxydiimide ring of metall...

A new series of dinuclear complexes [(Cp*M)2{(2-pyridyl)-C═C-(2-pyridyl)}Cl2] (M = Rh (1a), Ir (1b)) and tetranuclear metallamacrocycles [{(Cp*M)2{(2-pyridyl)-C═C-(2-pyridyl)}(pyrazine)}2](OTf)4 (M = Rh (2a), Ir (2b)), [{(Cp*M)2{(2-pyridyl)-C═C-(2-pyridyl)}(bpy)}2](OTf)4 (M = Rh (3a), Ir (3b); bpy = 4,4′-bipyridine), and [{(Cp*M)2{(2-pyridyl)-C═C-(2-pyridyl)}(bpe)}2](OTf)4 (M = Rh (4a), Ir (4b); 4,4′-bpe = trans-1,2-bis(4-pyridyl)ethylene) were constructed stepwise through double-site C–H activation on the olefinic C═C bond of 1,2-bis(2-pyridyl)ethylene. Isomers were observed in both the dinuclear species and tetranuclear macrocyclic complexes and were confirmed by single-crystal X-ray diffraction. The molecular structures of 1a–c, (R,R)-(S,S)-3b, (R,R)-(S,S)-4a, (R,R)-(R,R)-/(S,S)-(S,S)-4a, and (R,R)-(S,S)-4b were characterized by single-crystal X-ray crystallography. All complexes were fully characterized by 1H NMR spectroscopy, ESI-MS, and elemental analysis.

Single-crystal X-ray diffraction (SCD), X-ray fluorescence (XRF), inductively coupled plasma optical emission spectroscopy (ICP-OES) and X-ray excited luminescence (XEL) measurements were performed to investigate structure details and segregation coefficients of (Lu 1− x Y x ) 2 SiO 5 :Ce ( x =0 at%, 8.7 at%, 25.7 at%, 44.7 at%, 65.7 at%, 87.9 at% and 100 at%). Y 3+ cations were found to have a preferential occupation for RE 1 site (7-oxygen-coordinated) over RE 2 site (6-oxygen-coordinated), which results in a greater increase of cell parameter c than that of a with increase in Y content due to LYSO's microstructure characteristics. Results presented here revealed that the less the difference in electronegativity and effective ionic radius between the two ions, the easier substitution of one ion by the other, and hence the higher segregation coefficients. Besides, the contribution of luminescence of Ce1 and Ce2 in the whole XEL was evaluated, and the location of Ce 3+ ion was discussed.

Unusual chemical transformations such as three-component combination and ring-opening of N-heterocycles or formation of a carbon-carbon double bond through multiple C-H activation were observed in the reactions of Tp(Me2) -supported yttrium alkyl complexes with aromatic N-heterocycles. The scorpionate-anchored yttrium dialkyl complex [Tp(Me2) Y(CH2 Ph)2 (THF)] reacted with 1-methylimidazole in 1:2 molar ratio to give a rare hexanuclear 24-membered rare-earth metallomacrocyclic compound [Tp(Me2) Y(μ-N,C-Im)(η(2) -N,C-Im)]6 (1; Im=1-methylimidazolyl) through two kinds of C-H activations at the C2- and C5-positions of the imidazole ring. However, [Tp(Me2) Y(CH2 Ph)2 (THF)] reacted with two equivalents of 1-methylbenzimidazole to afford a C-C coupling/ring-opening/C-C coupling product [Tp(Me2) Y{η(3) -(N,N,N)-N(CH3 )C6 H4 NHCHC(Ph)CN(CH3 )C6 H4 NH}] (2). Further investigations indicated that [Tp(Me2) Y(CH2 Ph)2 (THF)] reacted with benzothiazole in 1:1 or 1:2 molar ratio to produce a C-C coupling/ring-opening product {(Tp(Me2) )Y[μ-η(2) :η(1) -SC6 H4 N(CHCHPh)](THF)}2 (3). Moreover, the mixed Tp(Me2) /Cp yttrium monoalkyl complex [(Tp(Me2) )CpYCH2 Ph(THF)] reacted with two equivalents of 1-methylimidazole in THF at room temperature to afford a trinuclear yttrium complex [Tp(Me2) CpY(μ-N,C-Im)]3 (5), whereas when the above reaction was carried out at 55 °C for two days, two structurally characterized metal complexes [Tp(Me2) Y(Im-Tp(Me2) )] (7; Im-Tp(Me2) =1-methyl-imidazolyl-Tp(Me2) ) and [Cp3 Y(HIm)] (8; HIm=1-methylimidazole) were obtained in 26 and 17 % isolated yields, respectively, accompanied by some unidentified materials. The formation of 7 reveals an uncommon example of construction of a CC bond through multiple C-H activations.

Two new trinuclear μ3 -bridged rare-earth metal phosphinidene complexes, [{L(Ln)(μ-Me)}3 (μ3 -Me)(μ3 -PPh)] (L=[PhC(NC6 H4 iPr2 -2,6)2 ](-) , Ln=Y (2 a), Lu (2 b)), were synthesized through methane elimination of the corresponding carbene precursors with phenylphosphine. Heating a toluene solution of 2 at 120 °C leads to an unprecedented ortho CH bond activation of the PhP ligand to form the bridged phosphinidene/phenyl complexes. Reactions of 2 with ketones, thione, or isothiocyanate show clear phospha-Wittig chemistry, giving the corresponding organic phosphinidenation products and oxide (sulfide) complexes. Reaction of 2 with CS2 leads to the formation of novel trinuclear rare-earth metal thione dianion clusters, for which a possible pathway was determined by DFT calculation.

A three-dimensional porous structure of [Zn7O2(bpdc)4(dmpp)2]·6DEF·10H2O (MAC-7, H2bpdc = 4,4'-biphenyldicarboxylic acid, Hdmpp = 3,5-dimethyl-4-(4'-pyridyl)pyrazole), built of 12-bridged carboxylate-pyrazolate shared Zn7O2 clusters, has been synthesized. Because of the presence of 12-bridged carboxylate-pyrazolate shared building block, MAC-7 is a double-linked pcu-type framework and shows reversible phase transformation. Photoluminescent property studies indicate that MAC-7 could sense nitrobenzene over toluene, p-xylene, and mesitylene by luminescent quenching.

Theseanalogies provide promising ideas for the self-assembly ofnovel supramolecular systems based on anion coordination.In the past few decades, zero-dimensional, aestheticallypleasing metal coordination complexes, such as molecularsquares, capsules, tetrahedra, and other complex polyhedralshapes, have attracted much interest.

The tridentate ligands, 4-R 1 -6-R 2 -2-{( trans -2-(isoindolin-2-yl)-1,2–diphenylethylimino) methyl}phenol (R 1 = R 2 = tert -butyl, 3a ; R 1 = Ph, R 2 = H, 3b ; R 1 = R 2 = H, 3c ; R 1 = R 2 = Cl, 3d ; R 1 = R 2 = Br, 3e ; R 1 = R 2 = I, 3f ) in which a substituted salicylaldiminato moiety and an isoindoline are linked by trans -1,2-diphenylethylene moiety have been prepared. Ligand 4-R 1 -6-R 2 -2-{( trans -2-(isoindolin-2-yl)-1,2–diphenylethylamino)methyl}phenol (R 1 = R 2 = tert -butyl, 4a ; R 1 = R 2 = I, 4f ) was obtained from the reduction of 3a and 3f with NaBH 4 in methanol/THF solution at low temperature. Deprotonation of these tridentate ligands 3a – f , 4a and 4f by NaH at −78 °C in THF, followed by treating with 1.2 equiv of TiCl 4 in toluene at room temperature, afforded the desired dark red titanium complexes[Ti(L)Cl 3 ] ( 5a – f , 6a and 6f ) in moderate to good yields. The structures of 5a and 6a were confirmed by single-crystal X-ray diffraction in the solid state. The metal atom has a distorted octahedral coordination geometry through the two nitrogen and one oxygen atoms from the tridentate ligand and three chlorides. These titanium complexes with such trans -1,2-diphenylethylene bridged tridentate ligands proved to be active to catalyze ethylene (co)polymerization with activity of 12.4–232.0 kg-polymer/mol(Ti)⋅h. The 13 C NMR analysis of the polymer produced revealed that the polymer is highly linear polyethylene with no detectable branches and only very low amount of 1-hexene was incorporated into the main chain of the polyethylene.

The chemisorption of gaseous HCl molecules in a two-dimensional coordination polymer results in subtle changes in its structure and instigates a drastic modification from antiferro- to ferromagnetic properties.

The selective and effective binding of secondary ammoniums with a weakly coordinating tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (BArF) counteranion by per-ethylated pillar[5,6]arenes is reported. The construction of a first pillararene-based self-sorting system consisting of two wheels and two axles is also described.

A pair of novel palladium complexes {[(1S,2S)-L]PdBr2} and {[(1R,2R)-L]PdBr2} of chiral di-N-heterocyclic carbene ligands derived from chiral 1,2-cyclohexanediamine have been prepared in moderate to good yields and characterized by NMR, HRMS and X-ray single crystal diffraction studies. The obtained chiral NHC–Pd compound was able to catalyze the asymmetric Suzuki–Miyaura couplings of aryl bromides with arylboronic acids in good yields and moderate enantioselectivities (up to 61% ee).

Reported herein is the FeCl3-promoted intermolecular sulfoesterification of o-(1-alkynyl)benzoates with disulfides, which provides a convenient and efficient method for synthesis of 4-sulfenylisocoumarins. Various functional groups such as methoxy, halides, ester, cyano and silicon groups in the substrates are tolerated, and heterocycle-fused chalcogenylpyrones are also successfully achieved directly from the corresponding heterocyclic precursors under the same reaction conditions. In addition, starting from diynylbenzoate, this reaction sequence can be combined with a bicyclization step leading to the tetracyclic (E)-3-(2-phenyl-3-phenylchalcogenylinden-1-ylidene)isobenzofuranone frameworks with high regiospecificity and exclusive trans stereoselectivity.

Cyanide group is a robust electron-mediate ligand, widely used in functional coordination polymers. Synthesis of cyanide-containing functional coordination polymersvia solvothermal in situ reaction is a new efficient approach. In this paper, four novel ternary coordination polymers, namely [Ag3(trz)2(CN)]n (1), [Ag3(detrz)2(CN)]n (2), [Ag4(dptrz)2(CN)2]n (3), [Ag3(dptrz)2(CN)]n (4) (Htrz = 1H-1,2,4-triazole, Hdetrz = 3,5-diethyl-1H-1,2,4-triazole, Hdptrz = 3,5-dipropyl-1H-1,2,4-triazole), were solvothermally synthesized and characterized. The cyanide groups are all in situ generated from C–C cleavage reaction of acetonitrile. The cyanide group acts as terminal group in 1, while as linker in 2, 3, 4. Phosphorescent properties of these in situ products are studied and compared with binary silver-triazole coordination polymers. The results show that phosphorescent emissions of 2, 3, and 4 are red-shifted compared to that of 1.

Three pillar[5]arene dimers, bridged by a flexible aliphatic chain (H1) or a relatively rigid phenylene unit (H2 and H3), were synthesized, with the possible synthetic strategies being discussed. The dimers could significantly enhance the binding affinities toward neutral model substrates in comparison with monomeric 1,4-dimethoxypillar[5]arene (H4) through the cooperative binding of two pillar[5]arene moieties. The molecular binding ability and selectivity are discussed from the viewpoints of the size/shape-fit concept and multiple recognition mechanism.

Two novel porous metal–organic frameworks {Zn7(btc)4(dmtrz)2(H2O)5}n (1) and {[Zn6(btc)4(dmtrz)3]·3H3O·2H2O}n (2) (H3btc = 1,3,5-benzenetricarboxylic acid, Hdmtrz = 3,5-dimethyl-1H-1,2,4-triazole) have been solvothermally synthesized. Single-crystal structure analysis reveals that both structure 1 and 2 contain special triazole-carboxylate shared paddle-wheel units. The crucial factors to the assembly of such paddle-wheel units are discussed. Gas adsorption studies suggest that 2 is a potential microporous material for adsorptive separation of CO2 over N2.

Organic nanotubes have been assembled from pillar[5]arenes 1 and 2. Compound 1 gelates organic solvents through the formation of tubular fibers which are evidenced by TEM and XRD experiments, while 2 assembles into two different channels under the template effect of water wires. In addition, the water wires in the nanotubes of 2 can be under selective proton conductance. The results described herein represent a new strategy for building tubular structures.

A novel three-dimensional (3D) [Ag3(dmtrz)2(CN)]n (1) with a three-fold interpenetrated CdSO4-type net is in situ solvothermal synthesized, and influential factors in the in situ reaction are briefly discussed. The luminescent property studies reveal that 1 shows green phosphorescent emission upon excitation while other binary silver(I)-dmtrz compounds discussed in this paper only emit blue phosphorescence.