|Budget Amount *help
¥4,100,000 (Direct Cost : ¥4,100,000)
Fiscal Year 2003 : ¥1,300,000 (Direct Cost : ¥1,300,000)
Fiscal Year 2002 : ¥2,800,000 (Direct Cost : ¥2,800,000)
The hydrindacene skeleton is constituted of a rigid aromatic ring and flexible five-membered rings. Functionalization by introducing various substituents at the positions along the XYZ axes offers the skeleton the opportunities to construct molecular devices with diverse properties. And, in 2,6-substituted derivatives, two less bulky groups on five-membered rings-are vertically oriented oa molecular plane.
(a)Preparation and properties of functionalized macrocycles.
The preparation and redox properties of the macrocycles containing multiple units of the (Z)-4,8-dimethoxyhydrindacene 1,that are connected at the 2,6-positions by butadiyne groups were studied. The trimer and tetramer exhibit reversible one-wave oxidation process similar to the monomer unit, 2,6-diethynylhydrindacene, while the dimer undergoes a reversible two-stage one-electron oxidation, which can be accounted for by the electronic interaction between the hydrindacene units.
(b)Preparation and properties of macrocycles constructed by reversible imine bonds.
The preparation of macrocycles by the imine-bond formation between (Z)-hydrindacenedialdehyde 2 and various aromatic diamines were studied. When a mixture of 2 and phenylenediamine 3a or 1,5-diaminonaphthalene 3b in CDC13 or C6D6 left at room temperature, aslightlysoluble macrocycles in a ratio of 2:3=2:2was formed predominantly. Thehost-guest properties of the reduced tetraamine macrocycles 3 were also studied.
(c)Construction of rotaxane structure using hydrindacene as the axle molecule.
In (E)-2, two less bulky formyl groups work as connecting parts with two terphenylamine half-rings by forming imine bonds. Then, the intramolecular macrocyclization of the imine derivative gave the precursor of the pseudo-rotaxane. It was revealed that imine bonds of the macrocycle were hydrolyzed under acidic condition, and the axle (E)-2 was dethreaded from macrecycle.