Kenshu Fujiwara

Entropy- and Hydrolytic-Driven Positional Switching of Macrocycle between Imine- and Hydrogen-Bonding Stations in Rotaxane-Based Molecular Shuttles

The construction and switching properties of a novel class of molecular shuttles 1 with imine-bonding stations for macrocyclic diamine parts are reported. Studies on dithioacetalized [2]rotaxane 4 with two hydrogen-bonding stations and a masked imine-bonding station showed that protonation of a macrocycle increases the shuttling barrier due to hydrogen-bond formation between NH 3 (+) groups and the TEG-stations. Hydrolysis of the imine-bonds of the imine-bridged molecular shuttles 1b, c with TEG-stations could exclusively give the [2]rotaxane 2b, c.2H (2+), with the macrocycle hydrogen-bonded with the TEG-station. In contrast, 1a without TEG-stations gave an equilibrated mixture of 1a, monoimine 3a.H (+), and 2a.2H (2+) under similar acidic hydrolytic conditions. The equilibrium between 1b, c and 2b, c.2H (2+) to control the position of the macrocycle could be successfully switched to either side by applying acidic hydrolytic or dehydrating conditions. Furthermore, the equilibrium was largely biased to [2]rotaxane 2b, c.2H (2+) under acidic hydrolytic conditions and could be reversed in favor of bis-imine 1b, c just by heating. This is a successful example of a molecular shuttle exhibiting entropy-driven translational isomerism with remarkable positional discrimination. An examination of thermodynamic parameters showed that imine-bond hydrolyses and the formation of hydrogen bonds between the macrocycle and the station are thermodynamically matched processes, because both processes are enthalpically favored and accompanied by a loss of entropy. The combination of imine-bonding and hydrogen-bonding station in a rotaxane system is the key to realizing the clear entropy-driven positional switching of the macrocycle observed.

Dynamic Molecular Propeller: Supramolecular Chirality Sensing by Enhanced Chiroptical Response through the Transmission of Point Chirality to Mobile Helicity

The secondary terephthalamide host 1a-H attached to four aryl blades was prepared from tetrabromide 2a by Suzuki-Miyaura coupling and undergoes a conformational change from a nonpropeller anti-form to a propeller-shaped syn-form upon complexation with ditopic guests such as p-xylylenediammonium derivatives (R,R)/(S,S)-3 (chirality generation). Through transmission of the point chiralities attached on the nitrogens in the chiral guests to the mobile helicity in 1a-H, the propeller-shaped host in the complex is biased to prefer a particular handedness (chirality biasing). While chiral guests with simple point chiralities such as (R,R)/(S,S)-3 exhibit only very weak CD activity, complexation with the dynamic propeller host 1a-H results in much stronger chiroptical signals (chiroptical enhancement). The chirality generation-chirality biasing protocol was successfully applied to a neurotransmitter, (-)-phenylephrine 4, acting as a chiral ditopic guest. When the chiral auxiliaries are attached to the host as in (R,R)-1b-H, complexation with (S,S)-3 causes CD enhancement but not with (R,R)-3, due to chiral recognition.

Ultralong Carbon–Carbon Bonds in Dispirobis(10‐methylacridan) Derivatives with an Acenaphthene, Pyracene, or Dihydropyracylene Skeleton

Acenapthalene, pyracene, and dihydropyracylene attached to two units of spiroacridan are a novel class of hexaphenylethane (HPE) derivatives that have an ultralong Csp3-Csp3 bond (1.77-1.70 A). These sterically challenged molecules were cleanly prepared by C-C bond formation through two-electron reduction from the less-hindered dications. These ultralong bonds were realized based on several molecular-design concepts including enhanced front strain through multiclamping by means of fusing or bridging aryl groups in the HPE molecule. The lengths of these ultralong bonds and their relation to the conformation (torsional angle) were also validated by means of theoretical calculations. Bond-fission experiments revealed that the bonds are more easily cleaved than standard covalent bonds to produce the corresponding dication upon oxidation with an increase in the length of the C-C bond.

Ultralong C-C bonds in hexaphenylethane derivatives

The longer C-C bond than the standard (1.54 Å) is so weakened that it is cleaved easily, as found in the parent hexaphenylethane (HPE). However, the compounds with an ultralong C-C bond (1.75 Å) can be isolated as stable solids when the bond-dissociated species does not undergo any reactions other than bond reformation. This is the central point in designing the highly strained HPEs, which were obtained by two-electron reduction of the corresponding dications. Steric repulsion of front strain is the major factor to expand the central C-C bond of HPEs. During the detailed examination of the ultralong C-C bond, the authors discovered the intriguing phenomenon of expandability: the C-C bond length can be altered over a wide range by applying only a small amount of energy (1 kcal mol-1) supplied by crystal packing force. This observation indicates that the much longer C-C bond than the shortest nonbonded contact (1.80 Å) will be realized under the rational molecular design concept.

Phenanthrene-4,5-diylbis(10-methylacridinium) with a short C[+]--C[+] contact: preparation, molecular structure, redox properties, and electrochromic interconversion with dihydropyrene derivative

The title dication (1 2+ ) was generated by oxidative bond cleavage of a 4,5-dihydoropyrene derivative (2) with two spiro(10-methylacridan) units. Despite the skewed deformation of the arylene spacer, two cationic chromophores in 1 2+ are forced to face in a proximity with a very short interatomic separation of 2.98(1) A between carbenium centers (X-ray), which makes the LUMO level of 1 much lower than that of biphenyl-2,2-diyl-type dication (3 2+ ).

Stereospecific change in conformation upon complexation of an exoditopic tetraamide host with a bis(ammonium) guest: chiral recognition and strong CD signaling.

Upon complexation of a rectangular-shaped achiral macrocyclic host with chiral guests, twisting deformation occurs to induce exciton-type bisignated CD, whereas a chiral rectangular host undergoes a similar structural change only with the matching enantiomer of a chiral guest.