ABSTRACT
This paper presents facile photoresponsive actuators comprising ferrocene as a guest chromophore and poly(butyl methacrylate) (PBMA) as a host matrix. The ferrocene-doped PBMA film exhibits mechanical expansion and contraction when a 445 nm laser is turned on and off, respectively. The photoresponsive film is attached by a commercially available acetylcellulose adhesive tape, which exhibits a bending motion that is controlled by turning the laser on and off. Thereafter, the double-layer film is employed to fabricate a table-shaped lifting machine (0.7 mg) that lifts a 10.5 mg object up and down by turning the laser on and off, respectively, and the mechanical force offered by the double-layer film is recorded. Additionally, the film is coated with gold and applied to an electric circuit that serves as a reversible photoresponsive switch. This film preparation technique is applied to other chromophores (e.g., Coumarin 343, Rhodamine 6G, Sudan Blue II, and Solvent Green 3) to independently control the motions of the films with 445, 520, and 655 nm lasers. The ferrocene-containing films also exhibit photoinduced healing from mechanical damage. Finally, the photoirradiation-accompanied morphological changes in the film are observed via small-angle X-ray scattering.
ABSTRACT
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.
ABSTRACT
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.
ABSTRACT
Molecular machines and switches composed of flexible pseudorotaxanes respond to external stimuli, transducing incident energy into mechanical motions. This study presents thermo- and photoresponsive dynamic pseudorotaxane crystals composed of axle molecules containing ferrocene or ruthenocene groups threaded through dibenzo[24]crown-8 ether rings. The ruthenocene-containing pseudorotaxane exhibits a crystal-to-crystal thermal phase transition at 86 °C, which is much lower than that of the ferrocene-containing pseudorotaxane (128 °C). Single-crystal X-ray crystallography at various temperatures reveals the details of the structural changes, and shows that the bulky ruthenocene provides distortion in the pseudorotaxane structure to facilitate twisting of the axle molecule. A mixed ferrocene and ruthenocene pseudorotaxane crystal is applied to photomechanical conversion under 405 nm laser irradiation at 85 °C and provides a lifting force 6,400-times the weight of the crystal itself upon phase transition.
ABSTRACT
Crystalline phase transitions caused by external stimuli have been used to detect physical changes in the solid-state properties. This study presents the mechanical switching of crystals of ferrocene-containing rotaxane controlled by focused laser light. The expansion and contraction of the crystals can be driven by turning on and off laser light at 445 nm. The irradiation-induced expansion of the crystal involves elongation along the a, b and c axes at 30 °C, whereas heating of the crystal at 105 °C causes the shortening of c axis. The expansions reversibly occur and have the advantage of a rapid relaxation (reverse) process. Single-crystal X-ray crystallography reveals the detailed structural changes of the molecules, corresponding to a change in the size of the crystals on laser irradiation. This molecular crystal behaviour induced by laser irradiation, is demonstrated for the remote control of objects, namely, microparticle transport and microswitching in an electric circuit.
ABSTRACT
A full-duplex fiber-to-the-X (FTTX)/radio-over-fiber (ROF) transport system based on a broadband amplified spontaneous emission (ASE) light source is proposed and demonstrated for rural wide-spread villages. Combining the concepts of long-transmission transmission and ring topology, a long-haul single-mode fiber (SMF) trunk is sharing with multiple rural villages. Externally modulated baseband (BB) (1.25 Gbps) and radio-frequency (RF) (622 Mbps/10 GHz) signals are successfully transmitted simultaneously. Good bit error rate (BER) performance was achieved to demonstrate the practice of providing wire/wireless connections for long-haul wide-spread rural villages. Since our proposed system uses only a broadband ASE light source to achieve multi-wavelengths transmissions, it also reveals an outstanding one with simpler and more economic advantages.
