Metastable Chiral Azobenzenes Stabilized in a Double Racemate

The self‐assembly of chiral organic chromophores is gaining huge significance due to the abundance of supramolecular chirality found in natural systems. We report an interdigitated molecular assembly involving axially chiral octabrominated perylenediimide (OBPDI) which transfers chiral information to achiral aromatic moieties. The crystalline two‐component assemblies of OBPDI and electron‐rich aromatic units were facilitated through π‐hole???π donor–acceptor interactions, and the charge‐transfer characteristics in the ground and excited states of the OBPDI cocrystals were established through spectroscopic and theoretical techniques. The OBPDI cocrystals entail a remarkable homochiral segregation of P and M enantiomers of both molecular entities in the same crystal system, leading to twisted double‐racemic arrangements. Synergistically engendered cavities with the stored chiral information of the twisted OBPDI stabilize higher‐energy P/M enantiomers of trans‐azobenzene through non‐covalent interactions.     

Palladium-Catalyzed Enantioselective Cacchi Reaction: Asymmetric Synthesis of Axially Chiral 2,3-Disubstituted Indoles

We report herein the first examples of a palladium-catalyzed enantioselective Cacchi reaction for the synthesis of indoles bearing a chiral C2-aryl axis. In the presence of a catalytic amount of Pd(OAc)₂ and (R,R)-QuinoxP* ligand, reaction of N-aryl(alkyl)sulfonyl-2-alkynylanilides with arylboronic acids under oxygen atmosphere afforded enantioenriched 2,3-disubstituted indoles in high yields and enantioselectivity. The indole ring is constructed de novo in this process and a complexation-induced chirality transfer is proposed to account for the observed enantioselectivity.     

Chiral Supramolecular Nanotubes of Single-Chain Magnets

We report a single-chain magnet (SCM) made of a terbium(III) building block and a nitronyl-nitroxide radical (NIT) functionalized with an aliphatic chain. This substitution is targeted to induce a long-range distortion of the polymeric chain and accordingly it gives rise to chains that are curled with almost 20 nm helical pitch. They self-organize as a chiral tubular superstructure made of 11 chains wound around each other. The supramolecular tubes have a 4.5 nm internal diameter. Overall, this forms a porous chiral network with almost 44 % porosity. Ab initio calculations highlight that each Tb^III ion possesses high magnetic anisotropy. Indeed, notwithstanding the supramolecular arrangement each chain behaves as a SCM. Magnetic relaxation with both finite and infinite-size regimes is observed and confirms the validity of the Ising approximation. This is associated with quite strong coercive field and magnetic remanence (H_c=2400 Oe M_R=2.09 μ_B at 0.5 K) for this class of compounds.     

Synthesis of Long Oxahelicenes by Polycyclization in a Flow Reactor

A series of oxahelicenes composed of ortho/meta-annulated benzene/pyridine and 2H-pyran rings were synthesized on the basis of the cobalt(I)-mediated (or rhodium(I)- or nickel(0)-mediated) double, triple, or quadruple [2+2+2] cycloisomerization of branched aromatic hexa-, nona-, or dodecaynes, thus allowing the construction of 6, 9, or 12 rings in a single operation. The use of a flow reactor was found to be beneficial for the multicyclization reactions. The stereogenic centers present in some of the oligoynes steered the helical folding in such a way that the final oxa[9]-, [13]-, [17]- and [19]helicenes were obtained in both enantiomerically and diastereomerically pure form. Specifically, the oxa[19]helicenes beat the current record in the length of a helicene backbone. Single-molecule conductivity was studied by the mechanically controllable break-junction method with a pyridooxa[9]helicene.     

Long-Range Chirality Recognition of a Polar Molecule on Au(111)

Chiral molecular self-assemblies were usually achieved using short-range intermolecular interactions, such as hydrogen-, metal–organic, and covalent bonding. However, unavoidable surface defects, such as step edges, surface reconstructions, or site dislocations may limit the applicability of short-range chirality recognition. Long-range chirality recognition on surfaces would be an appealing but challenging strategy for chiral reservation across surface defects at long distances. Now, long-range chirality recognition is presented between neighboring 3-bromo-naphthalen-2-ol (BNOL) stripes on an inert Au(111) surface across the herringbone reconstruction as investigated by STM and DFT calculations. The key to achieving such recognition is the herringbone reconstruction-induced local dipole accumulation at the edges of the BNOL stripes. The neighboring stripes are then forced to adopt the same chirality to create the opposite edged dipoles and neutralize the neighbored dipole moments.     

Asymmetric Cyclopropanation Catalyzed by Four Stereoisomers of a Copper-(Schiff-base) Complex with Double Chiral Centers

Catalytic asymmetric cyclopropanation of diazoacetates with olefins has attracted much attention. Those catalysts containing various metals and optically active ligands have been employed for this reaction1,2. The first catalytic asymmetric cyclopropanation reaction was reported in 1966 by Nozaki et al.3. The author used the copper(II) complex 1 bearing a salicyladimine ligand as catalyst though with a low e.e. value of 6%. Aratani and his coworkers designed the copper-(Schiff-base) comp…     

Effect of Molecular Weight on Photoinduced Birefringence in a Chiral Liquid Crystalline Azodye Polymer

Summary: The evolution of the photoinduced birefringence in thin films of narrow polymer fractions is studied and compared with the behavior of the non‐fractionated polymer. The Δn_ind value decreases by increasing the degree of polymerization ( ) within the oligomeric range but becomes independent of molecular weight starting from a of ≈70. Thermal pretreatment of the films results in higher photoinduced birefringence. The films show good stability of the photorecording.

Birefringence induced after 10 min, Δn_ind(600) and its growth rate at the same moment versus molecular weight.     

Colloid of Delaminated Layered Double Hydroxides： a Novel Type of LDH-based Catalyst

<正>The colloid of delaminated layered double hydroxides(LDHs),a new LDH-based catalyst,is described. The semi-heterogeneous delaminated colloidal MgPdAl-LDH,in which the total surface of catalytic site-bearing lamellae was rendered accessible for chemical reactivity,showed excellent catalysis toward Suzuki reaction.The turnover frequency of this catalyst for Suzuki reaction between bromobenzene and phenylboronic acid is about 8000 h~(-1).     

硫代硫酸根插层水滑石的层间限域反应

将无机阴离子硫代硫酸根(S2O23-)限域在锌铝水滑石(LDH)层间,并研究了其在水滑石层板限域空间内被铁氰根(Fe(CN)63-)氧化的反应过程.通过X射线衍射(XRD)和傅里叶变换红外(FTIR)光谱仪对反应的中间产物和最终产物进行的表征发现,氧化产物连四硫酸根(S4O62-)进入到溶液中,还原产物亚铁氰根(Fe(CN)64-)则保留在水滑石层间.进一步系统研究了该反应的动力学过程,考察了硫代硫酸根插层水滑石用量、铁氰化钾浓度和温度对反应的影响.结果表明该氧化还原反应符合球体内扩散模型.根据温度对反应速率影响,得出了该反应的表观活化能为24.6kJ.mol-1,比相同条件下溶液中反应活化能降低了约13.7kJ.mol-1.采用分子动力学(MD)模拟计算了水分子含量对硫代硫酸根插层水滑石层间距大小的影响.计算表明:在水溶液环境中,水滑石微反应器的尺寸在特定方向具有可调控性.根据实验表征和理论计算对该层间反应的机理进行了探讨.因此,该类层状材料可以作为一种新型纳米级微反应器应用于调控化学反应.     

Control of Intramolecular Hydrogen Bonding in a Conformation-Switchable Helical-Spring Polymer by Solvent and Temperature

A substituted poly(phenylacetylene) derivative (PPA_HB) with two hydroxymethyl groups at the meta position of the side phenyl ring was examined as a conformation-switchable helical spring polymer that responds to solvent and heat stimuli in a precisely controlled manner. Intramolecular hydrogen bonds, which cause the helical structure of the polymer, were broken and re-formed by adjusting the hydrogen-bonding strength values (pK_HB) of various combinations of solvents or by varying the temperature. In this process, a reversible conformational change from cis–cisoid to cis–transoid, accompanied by a phase transition in the form of a helix-coil transformation occurred, with the polymer exhibiting critical changes of color fading and recovery in specific environments. These results demonstrate that PPA_HB can be used as either a pK_HB indicator or a thermometer. The color changes of the polymer solution are described in detail based on spectroscopic analyses and thermodynamic considerations.