M/P Helicity Switching and Chiral Amplification in Double-Helical Monometallofoldamers.

Short-stranded double-helical monometallofoldamers capable of M/P-switching were constructed by the complexation of two strands, each with two L-shaped units linked by a 2,2'-bipyridine, with a Zn(II) cation. The helix terminals of the "double-helical form" folded by π-π interactions can unfold in solution to equilibrate with the "open forms" that are favored at higher temperatures. Interestingly, the helical chirality of the monometallofoldamers with chiral side chains induced a single-handed helix sense and controlled M/P-switching depending on achiral solvent stimuli. For instance, the (M)-helicity was favored in nonpolarized solvents (toluene, hexane, Et2O), whereas the (P)-helicity was favored in Lewis basic solvents (acetone, DMSO). Circular dichroism (CD) and rotating-frame overhauser enhancement spectroscopy (ROESY) measurements revealed that the conformational change of the chiral side chains due to interaction of Lewis basic solvents with the double helices induced helicity bias. These novel double-helical monometallofoldamers possessed a stable helical structure and exhibited switchable chiroptical properties (gabs ∼ 10-3-10-2). In addition, the chiral strand exhibited chiral transfer and amplification abilities through the formation of chiral heteroleptic double-helical monometallofoldamers when mixed with an achiral strand.

Umbrella-Shaped Amphiphiles: Internal Alkylation of an Aromatic Micelle and Its Impact on Cavity Features.

To develop new hybrid micelles with alkyl/polyaromatic core-shell structures, we synthesized umbrella-shaped amphiphiles bearing a bent anthracene dimer with a linear alkyl chain (i.e., octyl and hexadecyl groups). The amphiphiles quantitatively assemble into spherical micelles (~2-3 nm in core diameter), possessing an alkylated cavity surrounded by a polyaromatic framework, in water. The alkylation significantly enhances the stability of the micellar structures against dilution (up to 9 µM) and heat (up to >120 °C). The highly condensed hexadecyl core of the hybrid micelle, as indicated by solvatochromic guest probes, displays increased uptake ability toward large alkylated metallodyes. Interestingly, efficient uptake of aromatic macrocycles (i.e., [n]cycloparaphenylenes) by the present micelle provides pseudorotaxane-shaped host-guest composites with high emissivity (ΦF=up to 35 %). Internal multi-alkylation of an aromatic micelle can thus successfully enhance its assembly stability/guest uptake functions.

Recognition of Amino Acid Salts by Temperature-Dependent Allosteric Binding with Stereodynamic Urea Receptors.

Positive homotropic artificial allosteric systems are important for the regulation of cooperativity, selectivity and nonlinear amplification. Stereodynamic homotropic allosteric receptors can transmit and amplify induced chirality by the first ligand binding to axial chirality between two chromophores. We herein report stereodynamic allosteric urea receptors consisting of a rotational shaft as the axial chirality unit, terphenyl units as structural transmission sites and four urea units as binding sites. NMR titration experiments revealed that the receptor can bind two carboxylate guests in a positive homotropic allosteric manner attributed to the inactivation by intramolecular hydrogen-bonding between urea units within the receptor. In addition, the VT-CD spectra observed upon binding of the urea receptor with l- or D-amino acid salts in MeCN showed interesting temperature-dependent Cotton effects, based on the differences of the receptor shaft unit and the guest structure. The successful discrimination of hydrocarbon-based side chains of amino acid salts indicated that the input of chiral and steric information for the guest was amplified as outputs of the Cotton effect and the temperature-dependence of VT-CD spectra through cooperativity of positive allosteric binding.

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.

Dynamic Au-C σ-Bonds Leading to an Efficient Synthesis of [n]Cycloparaphenylenes (n = 9-15) by Self-Assembly.

The transmetalation of the digold(I) complex [Au2Cl2(dcpm)] (1) (dcpm = bis(dicyclohexylphosphino)methane) with oligophenylene diboronic acids gave the triangular macrocyclic complexes [Au2(C6H4) x (dcpm)]3 (x = 3, 4, 5) with yields of over 70%. On the other hand, when the other digold(I) complex [Au2Cl2(dppm)] (1') (dppm = bis(diphenylphosphino)methane) was used, only a negligible amount of the triangular complex was obtained. The control experiments revealed that the dcpm ligand accelerated an intermolecular Au(I)-C σ-bond-exchange reaction and that this high reversibility is the origin of the selective formation of the triangular complexes. Structural analyses and theoretical calculations indicate that the dcpm ligand increases the electrophilicity of the Au atom in the complex, thus facilitating the exchange reaction, although the cyclohexyl group is an electron-donating group. Furthermore, the oxidative chlorination of the macrocyclic gold complexes afforded a series of [n]cycloparaphenylenes (n = 9, 12, 15) in 78-88% isolated yields. The reorganization of two different macrocyclic Au complexes gave a mixture of macrocyclic complexes incorporating different oligophenylene linkers, from which a mixture of [n]cycloparaphenylenes with various numbers of phenylene units was obtained in good yields.

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.

Spacer-Dependent Cooperativity of Helicity in Fluorescent Bishelical Foldamers Based on L-Shaped Dibenzopyrrolo[1,2-a][1,8]naphthyridine.

For the construction of helical foldamers composed of π-frameworks, the choice of appropriate π-π stacking units and π-spacers connecting them is important. The transfer of helicity between the minimal helix structural units is also an essential factor in the construction of homochiral helical foldamers. Tetramers 4 a-4 d, which have four L-shaped dibenzopyrrolo[1,2-a]naphthyridine units, were synthesized to investigate the interplay and cooperativity of the helical structures. Tetramer 4 a bridged with a biphenyl unit formed a homochiral bishelical structure with π-π stacking between the L-shaped units (3.3 Å), consisting only of (P,P)- and (M,M)-enantiomers without the (P,M)-diastereomer, owing to interplay through the axial chirality of biphenyl unit in the solid state. Similarly, in solution, thermodynamic stabilization of the two helix formations worked cooperatively to favor the bishelical form of 4 a. Furthermore, bishelical foldamer 4 a emitted intense fluorescence (Φ=0.86).

Ring rotation of ferrocene in interlocked molecules in single crystals.

This work describes unique molecular motions of ferrocene-containing interlocked molecules observed by single-crystal X-ray crystallography. The rotational flexibility of ferrocene is achieved using combinations of ferrocene-tethered ammonium and 30-membered ring dibenzo-crown ether. By contrast, ferrocene was locked in the complex with an 18-membered ring dibenzo-crown ether and CH2Cl2. When the complex was heated at 358 K, CH2Cl2 was removed from the complex, which led to drastic structural changes, including a semieclipsed-to-disordered transition of ferrocene and flipping of the dibenzo-crown ether.

Sulphur-Embedded Hydrocarbon Belts: Synthesis, Structure and Redox Chemistry of Cyclothianthrenes.

Cyclothianthrenes, a series of sulphur-embedded hydrocarbon belts proposed a decade ago, were successfully constructed through a stepwise bottom-up synthesis. The belt [6]cyclothianthrene ([6]CT) is the smallest and most strained member of the family yet reported. Both [6]CT and [8]CT are the first examples of cyclothianthrene characterized by single crystal X-ray diffraction. An unprecedented chiral belt [7]CT and a Möbius-shaped [9]CT were also achieved via modular synthesis. Crystallographic and computational studies show that belts [6]CT-[8]CT have prism-like conformations with well-defined tubular cavities which have potential for guest molecule inclusion. Cyclic voltammograms further revealed that these belts are redox-active. The success of constructing sulphur-embedded hydrocarbon belts, that is, cyclothianthrenes, greatly enriches the chemistry of heteroatom-doped molecular belts and tubes.

Photoinduced Mechanical Motions of Pseudorotaxane Crystals Composed of Azobenzene and Ferrocenyl Groups on an Axle and a Crown Ether Ring.

This work describes the design and characterization of photoresponsive dynamic pseudorotaxane crystals composed of azobenzene and ferrocenyl groups in an ammonium cation axle component threaded through dibenzo[24]crown-8 ether rings. Pseudorotaxanes provide flexibility for cis and trans isomerization of azobenzene groups in a crystal state, enabling reversible bending motions under alternating 360 and 445 nm laser irradiation. For such bending motions, strained azobenzene structures were essential; these motifs were obtained by increasing the bulkiness of the substituents on the axle and ring molecules. In addition, the crystals showed photosalient effects, such as jumping motions, under 445 nm laser irradiation. These motions were assisted by the photoabsorption of the ferrocenyl group, which converted 445 nm laser light into heat. The maximum lifting weight accompanied by the photoinduced mechanical motion of a particular crystal was estimated to be 9600 times the crystal weight. These pseudorotaxane crystals exhibit promising features for applications in micro-nanometer-sized miniature mechanical devices.

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.

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.

Reversible Laser-Induced Bending of Pseudorotaxane Crystals.

This study investigated the dynamic photoresponse of pseudorotaxane crystals with azobenzene and ferrocenyl groups in the axle component. X-ray crystallography showed pseudorotaxanes with a methylazobenzene group and a dibromophenylene ring in the cyclic component to exhibit twisting of the trans-azobenzene groups at torsion angles of 17° and 38°, respectively. Repeated alternating laser irradiation of the crystals at 360 and 445 nm produced bending of 20-30° in opposite directions, with no evidence of decay. Under 445 nm irradiation, bending took place within 0.3 s. A crystal of nonsubstituted pseudorotaxane showed bending of only 2° under 360 nm irradiation due to multiple π-π interactions between the planar trans-azobenzene groups. The pseudorotaxane crystals have two chromophores, bent rapidly and reversibly on irradiation at rates depending on the molecular structure.

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.

[3]Rotaxane-based dinuclear palladium catalysts for ring-closure Mizoroki-Heck reaction.

[3]Rotaxane containing two Pd centers in the cyclic compounds catalyzes a Mizoroki-Heck reaction of substrates with two iodophenyl groups with bisacrylate. Formation of the cyclic products is enhanced by the rotaxane catalyst more smoothly than Pd(OAc)(2).