Tris-Azo Triangular Paraphenylenes: Synthesis and Reversible Interconversion into Radial π-Conjugated Macrocycles.

We report the synthesis of cycloparaphenylene derivatives featuring tris-azo groups. The smaller derivative, [3]cycloazobenzene, adopts a triangular all-cis form and exhibits thermally and photochemically stable characteristics due to significant ring strain as well as symmetric Kagome-patterned crystal packing. In contrast, the as-synthesized [3]cycloazobenzene with three biphenylene bridges adopts a triangular all-cis form, which undergoes photoinduced isomerization, leading to a photostationary state. Interestingly, the addition of an excess of acid selectively leads to the formation of an all-trans form. DFT calculations reveal that the interconversion from a triangular to a circular shape correlates with an increase in HOMO and a decrease in LUMO, characteristics intrinsic to radial π-conjugated systems.

Preparation of a Multicarbazole-Based Nanocapsule Capable of Largely Modulating Guest Spectroscopic Properties in Water.

A nanocapsule composed of multiple carbazole panels (ca. 12 panels) was quantitatively generated from bent carbazole-based amphiphiles in water. Unlike previously reported macrocycles and coordination cages bearing several carbazole panels, the resultant nanocapsule displays enhanced emissivity and improved electrochemical stability as compared with the monomeric amphiphile. The spectroscopic properties of substituted coumarin and boron-dipyrromethene dyes can be modulated upon encapsulation by the nanocapsule in water. In the cavity, a highly blue-shifted absorption band is observed from largely twisted coumarin dyes and two absorption bands are found from boron-dipyrromethene dimers stacked in an unusual L-shaped fashion. Moreover, the encapsulated dimers exhibit unique excimer-like emission.

A Macrocyclic Gold(I)-Biphenylene Complex: Triangular Molecular Structure with Twisted Au2 (diphosphine) Corners and Reductive Elimination of [6]Cycloparaphenylene.

The digold(I) complex [Au2 Cl2 (Cy2 PCH2 PCy2 )] reacts with 4,4'-diphenylene diboronic acid to form a triangular macrocyclic complex with twisted Au-P-C-P-Au groups at the three corners. The synthesis of the complex and its chemical oxidation produced [6]cycloparaphenylene ([6]CPP) in 59 % overall yield.

Dynamic properties of molecular tweezers with a bis(2-hydroxyphenyl)pyrimidine backbone.

4,6-Bis(2-hydroxyphenyl)-2-alkylpyrimidines with two anthryl or 9-ethylnylanthryl substituents at the positions para to the OH groups prefer a U-shaped conformation supported by two intramolecular OH⋅⋅⋅N hydrogen bonds in the solid state and in CDCl3 solution. The compound with a hexyl substituent on the pyrimidine group and two 9-ethynylanthryl arms at the hydroxyphenyl groups forms a 1:1 complex with 2,4,7-trinitrofluorenone. Its association constant K(a) was estimated to be 2100 M(-1) at 298 K, which is larger than those of other molecular tweezers (K(a) < 1000 M(-1)). DFT calculations suggested that the complex adopts a stable conformation supported by intramolecular hydrogen bonds among the OH groups and the pyrimidine ring as well as by intermolecular π-π interaction between the anthryl groups and 2,4,7-trinitrofluorenone. Addition of nBu4NF to a solution of the molecular tweezers or their complexes causes the cleavage of one or two OH⋅⋅⋅N hydrogen bonds, formation of new O⋅⋅⋅HF hydrogen bonds, and changes in the molecular conformation. The resulting structure of the molecular tweezers contains nonparallel anthryl groups, which do not bind the guest molecule. Photochemical measurements on 4,6-bis(2-hydroxyphenyl)-2-methylpyrimidine with two anthryl substituents showed negligible luminescence (quantum yield ϕ<0.01), owing to photoinduced electron transfer of the molecule with a U-shaped structure. However, the O-hexylated compound exhibits emission from the anthryl groups with ϕ=0.39.

Evaluation of the flocculation and de-flocculation performance and mechanism of polymer flocculants.

Understanding the interaction mechanism between polymeric flocculants and solid particles in two oppositely charged solutions: bentonite and calcium fluoride, is of great practical and fundamental importance. In this work, inorganic flocculants based on aluminum(III) or iron(III); cationic, anionic and non-ionic organic flocculants were used. The solution pH, which highly influenced the flocculation performance of the system, has been used as a function of turbidity removal, sediment volume and velocity. Results show that the flocculation of inorganic polymers does not depend on the zeta potential but on the solution pH, contrary for cationic and anionic polymers. Non-ionic polymer was independent on both. By varying the final pH of the heterogeneous solution formed of flocs-liquid, it was found for inorganic polymers, the optimum condition of pH < 3 to separate inorganic flocculant particles from flocs. Inductively coupled plasma atomic emission spectrometer and X-ray fluorescence analysis proved the reversibility of flocculation process by indicating the concentration of flocculant representative atom (Al or Fe) in the flocs and in the emerging solutions when the flocculation was optimized and the reversibility was effective. As results, weak forces were suggested as responsible for inorganic polymers flocculation where electrostatic interaction and hydrogen bonds may enroll the mechanism of organic flocculants.

A dodecamethoxy[6]cycloparaphenylene consisting entirely of hydroquinone ethers: unveiling in-plane aromaticity through a rotaxane structure.

[n]Cycloparaphenylenes ([n]CPPs, where n is the number of phenylene groups), consisting of 1,4-linked phenylene unit, have attracted much attention due to their cyclic π-conjugated structures and physical properties. However, functionalizing of the benzene rings of smaller [n]CPPs (n < 7) has been a challenge due to ring strain and steric hindrance of the substituents that hampers their synthesis. Here we show successful synthesis of a new [6]CPP derivative with twelve methoxy groups at the 2,5-positions of all benzene rings by utilizing our developed CPP synthesis method via a macrocyclic gold complex. This molecule exhibited a significantly higher oxidation potential caused by the electron-donating ability of the methoxy groups and the tubular molecular conformation, allowing facile oxidation to give dicationic species with in-plane aromaticity. Furthermore, this molecule successfully included with the guest molecules with a flexible alkyl chain in the cavity, enabling the creation of a CPP-based rotaxane, which exploited its mechanically interlocked molecular structure to the first experimental observation that the in-plane aromaticity in the center of the macrocycle.

Strained and unstrained macrocycles composed of carbazole and butadiyne units: electronic state and optical properties.

Cu(OAc)(2) catalyzes dehydrogenative condensation of 3,6-bis(2-ethynylphenyl)carbazole in the presence of O(2) to afford the cyclization product 1 and cyclodimer 2. Compound 1 contains bent carbazole and butadiyne groups, while 2 has a less strained structure with Z shape around the two parallel butadiyne groups. Optical properties of the compounds are discussed based on the electronic states estimated from electrochemical measurement and density functional theory calculation.

Digold(I) Thianthrenyl Complexes. Effect of Diphosphine Ligands on Molecular Structures in the Solid State and in Solution.

A series of digold complexes possessing two thianthrenyl ligands, Au2(Thi)2(Ph2P(CH2) n PPh2) (Thi: 1-thianthrenyl; 1: n = 1, 2: n = 2, 3: n = 3, 4: n = 4), were prepared and characterized by crystallographic and spectroscopic measurements. X-ray crystallography of complexes 1 and 3 revealed U-shaped structures with short Au-Au distances [3.2171(3) Å and 3.0735(2) Å]. Complex 2 and three of the four structure-determined molecules of complex 4 showed structures without Au-Au contacts. UV-vis spectroscopic measurements of 1-4 and TD-DFT calculations of the two conformers of 1 revealed that complexes 1 and 3 in the solution phase contained conformers with Au(I)-Au(I) interactions in a much higher proportion than complexes 2 and 4. As a result, complexes with diphosphine ligands containing an odd number of methylene groups preferred structures with Au-Au interactions in the solid state and in solution. Oxidation of 1 with 2 equiv of PhICl2 yielded a mixture of monomeric and dimeric thianthrenes and its dimer via ligand elimination and C-C coupling, respectively.

Tetrapalladium complex with bridging germylene ligands. Structural change of the planar Pd4Ge3 core.

A complex with a planar hexagonal Pd(4)Ge(3) core, [Pd{Pd(dmpe)}(3)(µ(3)-GePh(2))(3)], was synthesized and characterized by X-ray and NMR measurements as well as by DFT calculations. 4-tert-Butylbenzenethiol converted the Pd(4) complex into a hexapalladium complex, [{Pd(3)(µ-GePh(2))(2)(µ-H)(µ(3)-GePh(2)(SC(6)H(4)(t)Bu-4))}(2)(µ-dmpe)], composed of two Pd(3)Ge(3) units bridged by a dmpe ligand. The addition of CuI or AgI to the Pd(4) complex yielded [Pd(µ-MI){Pd(dmpe)}(3)(µ(3)-GePh(2))(3) ] (M = Cu, Ag), in which Cu or Ag bridges a Pd-Pd bond of the Pd(4)Ge(3) core. The CuI adducts in solution undergo a pivot motion of the CuI on the surface of the Pd(4)Ge(3) plane on the NMR time scale.

Aromatic macrocycle containing amine and imine groups: intramolecular charge-transfer and multiple redox behavior.

A cyclic compound that has alternating diphenylamine and quinodiimine units was obtained by condensation of anthraquinone with bis(4-aminophenyl)amine (aniline dimer) in 20% yield. The resulting macrocycle has an absorption of 462 nm, which is assigned to charge transfer transitions between electron-rich diphenylamine units and electron-poor anthraquinone diimine units. Cyclic voltammetry in acidic MeCN shows redox of anthraquinone diimine units (E(1/2) = 0.03 V vs Ag/Ag(+)) and of oxidation of amino groups of higher potentials (0.60 and 0.77 V).

Convenient synthesis of copper(I) halide quasi-one-dimensional coordination polymers: their structures and solid-state luminescent properties.

The heterogeneous reaction between copper(i) halide and pyridine derivative ligand in a suspension conveniently afforded luminescent copper(i) complexes. The progress of the reaction was confirmed by powder X-ray diffraction (PXRD) and thermogravimetric (TG) measurements. The structure of the obtained complexes was clarified by comparison with the X-ray analysis of a single crystal obtained by the homogeneous reaction in a solution. The reaction was affected by the type of solvent and substituents on the pyridine ligand. The reaction proceeded quantitatively, not depending on copper(i) halide, when ethyl acetate and 3-bromopyridine were used as the solvent and ligand, respectively. X-ray analysis of the single-crystals obtained by the corresponding reaction in solution revealed that the reaction in suspension afforded the same stair-shaped quasi-one-dimensional structure. The obtained copper(i) complex powders displayed luminescence, which was attributed to the halide/metal-to-ligand charge transfer (XMLCT), as elucidated by crystal orbital distribution and principal component of excitation based on density functional theory (DFT) calculations.

Bimolecular fusion of [Pd3(µ-CN-C6H3Me2-2,6)3(CN-C6H3Me2-2,6)3] induced by Ph2GeH2: formation of the redox-active Pd6Ge2 complex.

The reaction of Ph2GeH2 with a planar tripalladium(0) complex, [Pd3(µ-CN-C6H3Me2-2,6)3(CN-C6H3Me2-2,6)3], selectively afforded a hexagonal bipyramidal Pd6Ge2 complex, [Pd6(µ-GePh2)2(CN-C6H3Me2-2,6)8(µ-CN-C6H3Me2-2,6)2]. The molecule is stabilized by bridging coordination of isonitrile and GePh2 ligands, although all the Pd-Pd bonds are weak, as revealed by DFT calculations. The resulting complex undergoes two successive redox processes at E1/2 = -1.35 and -1.03 V (vs. Fc+/Fc), which correspond to the stepwise oxidation of the Pd(0)6 complex.

A rhomboid-shaped organic host molecule with small binding space. Unsymmetrical and symmetrical inclusion of halonium ions.

A shape persistent rhomboid-shaped organic host molecule having two pyridyl units was synthesized which induces size selective halonium inclusion. Cl(+) and Br(+) are included to form unsymmetric and symmetric complexes, while I(+) does not form a stable complex. The difference among the haloniums was ascribed to the matching (or mismatching) of the shape of the cavity and the guest ions. The complexation of the host molecule with other cations, such as Ag(+), Pd(2+), Zn(2+) and H(+), is also mentioned.

Columnar self-assembly of rhomboid macrocyclic molecules via step-like intermolecular interaction. Crystal formation and gelation.

Two macrocyclic compounds with a rhomboid molecular shape, composed of a π-conjugated framework and an imine or amine functionality, were synthesized. The amine-containing macrocycle crystallizes with step-like interaction of each molecule, forming a columnar arrangement, although dispersion of the imine gelates upon ultrasonification.