A Silver Nanocluster Assembled by a Superatomic Building Unit.

A unique assembly of a two-electron superatom, [Ag10{S2P(OiPr)2}8], as a primary building unit in the construction of a supramolecule [Ag10{S2P(OiPr)2}8]2(µ-4,4'-bpy) through a 4,4'-bipyridine (4,4'-bpy) linker is reported. This approach is facilitated by an open site in the structure that allows for effective pairing. The assembled structure demonstrates a minimal solvatochromic shift across organic solvents with variable polarities, highlighting the influence of self-assembly on the photophysical properties of silver nanoclusters.

Homoleptic Silver-Rich Trimetallic M20 Nanocluster.

Two silver-rich M20 alloy nanoclusters (NCs), [Cu3.5Ag16.5{S2P(OnPr)2}12] (1) and [Cu2.5AuAg16.5{S2P(OnPr)2}12] (2), were synthesized and fully characterized by electrospray ionization mass spectrometry, NMR spectroscopy, and X-ray crystallography. Cluster 2, the first structurally characterized trimetallic M20 NC, was produced by doping one Au atom into a bimetallic M20 NC. Structural analyses showed the preferred positions of Group 11 metals in the yielded M20 NCs. Their antioxidation ability has been investigated, and the time-dependent UV-vis spectrum shows that the presence of CuI atoms in structures 1 and 2 can improve the antioxidant ability.

A New Synthetic Methodology in the Preparation of Bimetallic Chalcogenide Clusters via Cluster-to-Cluster Transformations.

A decanuclear silver chalcogenide cluster, [Ag10(Se){Se2P(OiPr)2}8] (2) was isolated from a hydride-encapsulated silver diisopropyl diselenophosphates, [Ag7(H){Se2P(OiPr)2}6], under thermal condition. The time-dependent NMR spectroscopy showed that 2 was generated at the first three hours and the hydrido silver cluster was completely consumed after thirty-six hours. This method illustrated as cluster-to-cluster transformations can be applied to prepare selenide-centered decanuclear bimetallic clusters, [CuxAg10-x(Se){Se2P(OiPr)2}8] (x = 0-7, 3), via heating [CuxAg7-x(H){Se2P(OiPr)2}6] (x = 1-6) at 60 °C. Compositions of 3 were accurately confirmed by the ESI mass spectrometry. While the crystal 2 revealed two un-identical [Ag10(Se){Se2P(OiPr)2}8] structures in the asymmetric unit, a co-crystal of [Cu3Ag7(Se){Se2P(OiPr)2}8]0.6[Cu4Ag6(Se){Se2P(OiPr)2}8]0.4 ([3a]0.6[3b]0.4) was eventually characterized by single-crystal X-ray diffraction. Even though compositions of 2, [3a]0.6[3b]0.4 and the previous published [Ag10(Se){Se2P(OEt)2}8] (1) are quite similar (10 metals, 1 Se2-, 8 ligands), their metal core arrangements are completely different. These results show that different synthetic methods by using different starting reagents can affect the structure of the resulting products, leading to polymorphism.

Carbodicarbene: geminal-Bimetallic Coordination in Selective Manner.

The reaction of Pd(OAc)2 with free carbodicarbene (CDC) generates a Pd acetate trinuclear complex 1 via intramolecular C(sp3 )-H bond activation at one of the CDC methyl side arms. The solid structure of 1 reveals the capability of CDC to facilitate a double dative bond with two palladium centers in geminal fashion. This is attributed to the chelating mode of CDC, which can frustrate π-conjugation within the CDC framework. Such effect maybe also amplified by ligand-ligand interaction. The formation of other gem-bimetallic Pd-Pd, Pd-Au, and Ni-Au provides further structural evidence for this proof-of-concept in selective installation. Structural analysis is supported by computational calculations based on state-of-the-art energy decomposition analysis (EDA) in conjunction with natural orbitals for chemical valence (NOCV) method.

Interface-Controlled Synthesis of Au-BINOL Hybrid Nanostructures and Mechanism Study.

The combined functionality of components in organic-inorganic hybrid nanomaterials render them efficient nanoreactors. However, the development in this field is limited due to a lack of synthetic avenues and systematic control of the growth kinetics of hybrid structures. In this work, we take advantage of an ionic switch for regio-control of Au-BINOL(1,1'-Bi-2-naphthol) hybrid nanostructures. Aromatic BINOL molecules assemble into nanospheres, concomitant with the growth of the Au nanocrystals. The morphological evolution of Au nanocrystals is solely controlled by the presence of halides in the synthetic system. Here we show that quaternary ammonium surfactants (CTAB or CTAC), not only bridging Au and BINOL, but also contributing to the formation of concentric or eccentric structures when their concentrations are tuned to the range of 10-5 to 10-3 M. This facile strategy offers the potential advantage of scalable production, with diverse functional organic-inorganic hybrid nanocomposites being produced based on the specific archetype of Au-BINOL hybrid nanocomposites.

High-Temperature, High-Pressure Hydrothermal Synthesis of Ba3[B6O10(OH)2](CO3) and Ba6[B12O21(OH)2](CO3)2, Two Barium Borate Carbonates with 2D Layer and 3D Framework Structures.

Two new barium borate carbonates, Ba3[B6O10(OH)2](CO3) (1) and Ba6[B12O21(OH)2](CO3)2 (2), have been synthesized by high-temperature, high-pressure hydrothermal methods at 460 °C and 600 bar and structurally characterized by single-crystal X-ray diffraction, TGA, IR, and MAS 11B NMR spectroscopy. The descriptors of the fundamental building blocks (FBB) of both structures are 2Δ4□:⟨Δ2□⟩=⟨4□⟩=⟨Δ2□⟩. The FBB of 1 has a chair conformation, and the FBBs of 2 have both chair and boat conformations. Compound 1 adopts a noncentrosymmetric 2D layer structure with the Ba2+ cations and CO32- anions between the layers, whereas compound 2 has a centrosymmetric 3D framework structure containing 9- and 10-ring channels with the Ba2+ cations and CO32- anions at the center or on the edges of the channels. The two structures are two of the few examples where the carbonate groups are isolated and occupy their own independent sites.

A Series of Organic-Inorganic Hybrid Zinc Phosphites Containing Extra-Large Channels.

A series of organic-inorganic hybrid zinc phosphites with extra-large channels were synthesized and characterized by single-crystal X-ray diffraction. This is an unusual example of introducing 1,4-benzenedicarboxylate and/or biphenyl-4,4'-dicarboxylate ligands into the organically templated metal phosphite system to build extra-large-channel zeolite-related materials via hydro(solvo)thermal reactions. Those frameworks are composed of carboxylate linkers and inorganic tubes of zinc phosphites, translating their channel windows from a square shape (NTOU-1) to rhombus forms (NTOU-2 and NTOU-3) via the replacement of organic amines or ligands under synthesis conditions otherwise identical with those used to prepare NTOU-1. The synthesis, structural diversity, photoluminescence, and adsorption properties for dye molecules and lanthanide ions are also reported.

Carbodicarbenes: Unexpected π-Accepting Ability during Reactivity with Small Molecules.

An investigation of carbodicarbenes, the less explored member of the carbenic complex/ligand family has yielded unexpected electronic features and concomitant reactivity. Observed 1,2-addition of E-H bonds (E = B, C, Si) across the carbone central carbon and that of the flanking N-heterocyclic carbene (NHC) fragment, combined with single-crystal X-ray studies of a model Pd complex strongly suggests a significant level of π-accepting ability at the central carbon of the NHC moiety. This feature is atypical of classic NHCs, which are strong σ-donors, with only nominal π-accepting ability. The unanticipated π-acidity is critical for engendering carbodicarbenes with reactivity more commonly observed with frustrated Lewis pairs (FLPs) rather than the more closely related NHCs and cyclic (alkyl)(amino)carbenes (CAACs).

Two Polymorphs of an Organic-Zincophosphate Incorporating a Terephthalate Bridging Ligand in an Unusual Bonding Mode.

Two new polymorphs of a zinc phosphate incorporating the terephthalate organic ligand 1,4-benzenedicarboxylate (BDC), (H2DA)Zn2(cis-BDC)(HPO4)2 (1) and (H2DA)Zn2(trans-BDC)(HPO4)2 (2), where DA = 1,7-diaminoheptane, were synthesized via a hydro(solvo)thermal method at different reaction temperatures and structurally characterized by single-crystal X-ray diffraction. Interestingly, the BDC ligands, which adopt the bis-monodentate coordination model with a unusual cis type for compound 1 and with a trans linkage for compound 2, bridge the Zn atoms of the inorganic layers in the generation of two polymorphs with structural diversities (one kind of arrangement of the layered zincophosphate layer in 1; the flat and zigzag sheets of inorganic networks in 2). A simple method for tuning the optical luminescence of the title compound from blue, red, green, yellow, and pink to white emission by stirring powdered samples in lanthanide-cation-containing aqueous ethanol solutions at room temperature for 1-2 h is also presented.

Synthesis of d-Galactosamine and d-Allosamine Derivatives via a Microwave-Assisted Preparation of 1,6-Anhydroglucosamine.

We report a microwave-assisted intramolecular anomeric protection (iMAP) of glucosamine, which facilitates concise transformation of 1,6-anhydroglucosamine into 1,6-anhydrogalactosamine and 1,6-anhydroallosamine. The iMAP simultaneously obviates both the O1 and O6 protection, and the differentiation between O3 and O4 can be well-controlled by the N2 functionality because of the hydrogen bonding between N2 and O4. Epimerization of O4 afforded the galactosamine derivative and that of O3 yielded allosamine.

3-Iodo-1H-pyrazolo-[3,4-b]pyridine.

The title compound, C6H4IN3, is essentially planar, with a dihedral angle of 0.82 (3)° between the planes of the pyridine and pyrazole rings. In the crystal, pairs of mol-ecules are connected into inversion dimers through N-H⋯N hydrogen bonds. C-I⋯N halogen bonds link the dimers into zigzag chains parallel to the b-axis direction. The packing also features π-π stacking inter-actions along (110) with inter-planar distances of 3.292 (1) and 3.343 (1) Å, and centroid-centroid distances of 3.308 (1) and 3.430 (1) Å.

4-(1H-Pyrrolo-[2,3-b]pyridin-2-yl)pyridine.

The asymmetric unit of the title compound, C12H9N3, contains two independent mol-ecules in which the dihedral angle between the pyridine and aza-indole rings are 8.23 (6) and 9.89 (2)°. In the crystal, both types of mol-ecule are connected by pairs of N-H-N hydrogen bonds into inversion dimers.

N-(Pyrazin-2-yl)-1,8-naphthyridin-2-amine.

There are two independent mol-ecules in the asymmetric unit of the title compound, C12H9N5, in which the C-N(amine)-C angles differ slightly [129.63 (11) and 132.02 (11)°]. In each independent mol-ecule, an intra-molecular C-H⋯N hydrogen bond stabilizes the mol-ecular structure, forming an S(6) ring motif. The independent mol-ecules are linked via an N-H⋯N hydrogen bond. Further N-H⋯N and C-H⋯N hydrogen bonds connect the mol-ecules into chains along c axis. Pairs of C-H⋯π inter-actions between the chains lead to sheets parallel to the b axis. These are linked by π-π inter-actions between the naphthyridine and pyrazine rings [centroid-centroid separations of 3.553 (8) Å] into a three-dimensional supra-molecular network.

2-(1H-Pyrrolo-[2,3-b]pyridin-2-yl)pyridine.

In the title compound, C(12)H(9)N(3), the dihedral angle between the pyridine and aza-indole rings is 6.20 (2)°. In the crystal, pairs of N-H⋯N hydrogen bonds link mol-ecules into inversion dimers.

Bis(morpholin-4-ium) tetra-chlorido-cobalt(II).

The title compound, (C(4)H(10)NO)(2)[CoCl(4)], is an ionic compound consisting of two protonated tetra-hydro-1,4-oxazine (morpholine) cations and a [CoCl(4)](2-) dianion. The Co(II) ion is in a tetra-hedral coordination geometry. The cations exhibit chair-shaped conformations. A three-dimensional supra-molecular architecture is formed through N-H⋯Cl and C-H⋯Cl hydrogen bonds between the dianions and the cations.

2-(9,9-Diethyl-9H-fluoren-2-yl)-1-benzofuran.

In the title compound, C(25)H(22)O, the dihedral angle between the benzofuran and fluorene ring systems is 9.06 (6)°, and that between the two benzene rings of the fluorene system is 1.78 (12)°. Weak inter-molecular C-H⋯π inter-actions help to stabilize the crystal structure.

7-Hy-droxy-indan-1-one.

In the title compound, C(9)H(8)O(2), an intra-molecular O-H⋯O hydrogen bond generates an S(6) ring. The dihedral angle between the mean plane of the S(6) ring and the benzene ring is 1.89 (2)°. In the crystal, inversion-related mol-ecules are linked by pairs of O-H⋯O hydrogen bonds, forming a cyclic dimers with R(2) (2)(12) graph-set motif. Weak inter-molecular C-H⋯O(carbon-yl) and C-H⋯O(hy-droxy) hydrogen bonds link the dimers into chains along [010], generating two C(6) motifs that overlap three C atoms, forming R(2) (2)(8) ring motifs.

Low-Cost Hole-Transporting Materials Based on Carbohelicene for High-Performance Perovskite Solar Cells.

Two hole-transporting materials (HTMs) based on carbohelicene cores, CH1 and CH2, are developed and used in fabricating efficient and stable perovskite solar cells (PSCs). Owing to the rigid conformation of the helicene core, both compounds possess unique CH-π interactions in the crystalline packing pattern and good phase stability, which are distinct from the π-π intermolecular interactions of conventional planar and spiro-type molecules. PSCs based on CH1 and CH2 as HTMs deliver excellent device efficiencies of 19.36 and 18.71%, respectively, outperforming the control device fabricated with spiro-OMeTAD (18.45%). Furthermore, both PSCs exhibit better ambient stability, with 90% of initial performance retained after aging with a 50-60% relative humidity at 25 °C for 500 h. Due to the low production cost of both compounds, these newly designed carbohelicene-type HTMs have the potential for the future commercialization of PSCs.

4,4'-Bis(2,2,2-trifluoroethoxymethyl)-2,2'-bipyridine.

As part of a homologous series of novel polyfluorinated bipyridyl (bpy) ligands, the title compound, C(16)H(14)F(6)N(2)O(2), contains the smallest fluorinated group, viz. CF(3). The molecule resides on a crystallographic inversion centre at the mid-point of the pyridine C(ipso)-C(ipso) bond. Therefore, the bpy skeleton lies in an anti conformation to avoid repulsion between the two pyridyl N atoms. Weak intramolecular C-H...N and C-H...O interactions are observed, similar to those in related polyfluorinated bpy-metal complexes. A pi-pi interaction is observed between the bpy rings of adjacent molecules and this is probably a primary driving force in crystallization. Weak intermolecular C-H...N hydrogen bonding is present between one of the CF(3)CH(2)- methylene H atoms and a pyridyl N atom related by translation along the [010] direction, in addition to weak benzyl-type C-H...F interactions to atoms of the terminal CF(3) group. It is of note that the O-CH(2)CF(3) bond is almost perpendicular to the bpy plane.

[4-(1-Benzofuran-2-yl)phen-yl]diphenyl-amine.

The asymmetric unit of the title compound, C(26)H(19)NO, contains two mol-ecules. The dihedral angles between the benzofuran and benzene rings are 5.09 (8), 59.02 (8) and 67.74 (8)° in one mol-ecule and 18.70 (8), 52.78 (8) and 41.74 (8)° in the other. Weak inter-molecular C-H⋯π inter-actions help to stabilize the molecular structure .