A Silver Nanocluster Assembled by a Superatomic Building Unit.

A unique assembly of a two-electron superatom, [Ag{SP(OPr)}], as a primary building unit in the construction of a supramolecule [Ag{SP(OPr)}](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 M Nanocluster.

Two silver-rich M alloy nanoclusters (NCs), [CuAg{SP(OPr)}] () and [CuAuAg{SP(OPr)}] (), were synthesized and fully characterized by electrospray ionization mass spectrometry, NMR spectroscopy, and X-ray crystallography. Cluster , the first structurally characterized trimetallic M NC, was produced by doping one Au atom into a bimetallic M NC. Structural analyses showed the preferred positions of Group 11 metals in the yielded M NCs.

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

A decanuclear silver chalcogenide cluster, [Ag(Se){SeP(OPr)}] () was isolated from a hydride-encapsulated silver diisopropyl diselenophosphates, [Ag(H){SeP(OPr)}], under thermal condition. The time-dependent NMR spectroscopy showed that 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, [CuAg(Se){SeP(OPr)}] (x = 0-7, ), via heating [CuAg(H){SeP(OPr)}] (x = 1-6) at 60 °C.

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

Two hole-transporting materials (HTMs) based on carbohelicene cores, and , 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 and as HTMs deliver excellent device efficiencies of 19.

Carbodicarbene: geminal-Bimetallic Coordination in Selective Manner.

The reaction of Pd(OAc) with free carbodicarbene (CDC) generates a Pd acetate trinuclear complex 1 via intramolecular C(sp )-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.

Zn(II) and Co(II) derivatives anchored with scorpionate precursor: Antiproliferative evaluation in human cancer cell lines.

A 'scorpionate' type precursor [bdtbpza = bis(3,5-di-t-butylpyrazol-1-yl)acetate] has been employed to synthesize two mononuclear Zn and Co derivatives, namely [Zn(bdtbpza) (HO)]·2.5CHOH·2[(CH)C-CHN-C(CH)] (1) and [Co(bdtbpza)(CHOH)] (2) in good yield. Single crystal X-ray diffraction analysis reveals that in 1, the Zn atom is tetrahedrally surrounded by a pair of O atoms of two bis(pyrazol-1-yl)acetate units and two water molecules; while in 2, the Co atom shows an octahedral environment coordinating a pair of O atoms of two bis(pyrazol-1-yl)acetate units along with four methanol molecules.

Spectroelectrochemical studies of the redox active tris[4-(triazol-1-yl)phenyl]amine linker and redox state manipulation of Mn(ii)/Cu(ii) coordination frameworks.

This work describes the successful incorporation of a redox active linker, tris(4-(1H-1,2,4-triazol-1-yl)phenyl)amine (TTPA) into Mn(ii)/Cu(ii) based coordination frameworks. Solution state in situ spectroelectrochemistry of EPR and UV/Vis/NIR of the TTPA ligand were measured to gain a deeper understanding of the charge delocalization of the triphenylamine backbone. The assignments of the absorption bands for the radical cations in UV/Vis/NIR spectroelectrochemistry were supported by DFT calculations.

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.

High-Temperature, High-Pressure Hydrothermal Synthesis of Ba[BO(OH)](CO) and Ba[BO(OH)](CO), Two Barium Borate Carbonates with 2D Layer and 3D Framework Structures.

Two new barium borate carbonates, Ba[BO(OH)](CO) (1) and Ba[BO(OH)](CO) (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 B 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.

Hydrogen bonding and fluorous weak interactions in the non-isomorphous {4,4'-bis[(2,2,3,3-tetrafluoropropoxy)methyl]-2,2'-bipyridine-κN,N'}dibromidopalladium and -platinum complexes.

The polyfluorinated title compounds, [MBr(CHFNO)] or [4,4'-(HCFCFCHOCH)-2,2'-bpy]MBr, (1) (M = Pd and bpy is bipyridine) and (2) (M = Pt), have -CHOCHCFCFH side chains with methylene H-atom donors at the α and β sites, and methine H-atom donors at the terminal sites, in addition to aromatic H-atom donors. In contrast to the original expectation of isomorphous structures, (1) crystallizes in the space group C2/c and (2) in P2/n, with similar unit-cell volumes and Z = 4. The asymmetric unit of (1) is one half of the molecule, which resides on a crystallographic twofold axis.

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.

Side-chain conformations in the isomorphous polyfluorinated {4,4'-bis[(2,2-difluoroethoxy)methyl]-2,2'-bipyridine-κN,N'}dichloridopalladium and -platinum complexes.

The polyfluorinated title compounds, [MCl(CHFNO)] or [4,4'-(HCFCHOCH)-2,2'-bpy]MCl [M = Pd, (1), and M = Pt, (2)], have -C(H)OC(H)CFH side chains with H-atom donors at the α and β sites. The structures of (1) and (2) are isomorphous, with the nearly planar (bpy)MCl molecules stacked in columns. Within one column, π-dimer pairs alternate between a π-dimer pair reinforced with C-H.

Weak hydrogen and halogen bonding in 4-[(2,2-difluoroethoxy)methyl]pyridinium iodide and 4-[(3-chloro-2,2,3,3-tetrafluoropropoxy)methyl]pyridinium iodide.

To enable a comparison between a C-H...

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.

Molecular structures of 3-[(2,2,3,3-tetrafluoropropoxy)methyl]- and 3-[(2,2,3,3,3-pentafluoropropoxy)methyl]pyridinium saccharinates.

The salts 3-[(2,2,3,3-tetrafluoropropoxy)methyl]pyridinium saccharinate, CHFNO·CHNOS, (1), and 3-[(2,2,3,3,3-pentafluoropropoxy)methyl]pyridinium saccharinate, CHFNO·CHNOS, (2), i.e. saccharinate (or 1,1-dioxo-1λ,2-benzothiazol-3-olate) salts of pyridinium with -CHOCHCFCFH and -CHOCHCFCF meta substituents, respectively, were investigated crystallographically in order to compare their fluorine-related weak interactions in the solid state.

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), (HDA)Zn(cis-BDC)(HPO) (1) and (HDA)Zn(trans-BDC)(HPO) (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.

Weak hydrogen bonding and fluorous interactions in the chloride and bromide salts of 4-[(2,2,3,3-tetrafluoropropoxy)methyl]pyridinium.

Neutralization of 4-[(2,2,3,3-tetrafluoropropoxy)methyl]pyridine with hydrohalo acids HX (X = Cl and Br) yielded the pyridinium salts 4-[(2,2,3,3-tetrafluoropropoxy)methyl]pyridinium chloride, CHFNO·Cl, (1), and 4-[(2,2,3,3-tetrafluoropropoxy)methyl]pyridinium bromide, CHFNO·Br, (2), both carrying a fluorous side chain at the para position of the pyridinium ring. Single-crystal X-ray diffraction techniques revealed that (1) and (2) are isomorphous. The halide anions accept four hydrogen bonds from N-H, ortho-C-H and CF-H groups.

Near-Infrared-Absorbing and Dopant-Free Heterocyclic Quinoid-Based Hole-Transporting Materials for Efficient Perovskite Solar Cells.

New heterocyclic quinoid-based hole transporting materials (HTMs) with a rigid quinoid core [3,6-di(2H-imidazol-2-ylidene)cyclohexa-1,4-diene] have been synthesized. The new HTMs have good hole mobility (>10  cm  V  s ) and very intense absorption in the near-infrared region extending to >800 nm. High performance perovskite solar cells can be fabricated using these HTMs without dopant.

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.

Synthesis, structure, and catecholase activity of bispyrazolylacetate copper(II) complexes.

A series of six-coordination copper(ii) complexes containing bis(3,5-di-t-butylpyrazol-1-yl)acetate (bdtbpza) and N-heterocycles or chelating aliphatic ligands have been synthesized. The steric bulkiness of bis(pyrazol-1-yl)acetate anchors two bdtbpza to situate a trans position and to adopt an O-bound monodentate coordination mode with other nitrogen bases occupying the basal plane. Five mononuclear mixed ligand complexes, [Cu(bdtbpza)2(py)4] , [Cu(bdtbpza)2(t-Bupy)4] , [Cu(bdtbpza)2(pym)2(MeOH)2] , [Cu(bdtbpza)2(eda)2] , [Cu(bdtbpza)2(tmeda)(H2O)2] , where py = pyridine, t-Bupy = tert-butylpyridine, pym = pyrimidine, eda = ethylenediamine, and tmeda = tetramethylethylenediamine, were isolated and thoroughly characterized.

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.

Structure and emission studies of dimorphic crystals of [PtBr2(5,5'-bis(CF3CH2OCH2)-2,2'-bpy)] (1).

The yellow (1y) and orange (1o) crystalline polymorphs of [PtBr2(5,5'-bis(CF3CH2OCH2)-2,2'-bipyridine)] exhibit surprisingly short nearest neighbour Pt···Pt separations of 3.526 Å and 3.590 Å, respectively, at 295 K.

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)°.

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)°].