Fei Tong

Analysis of reaction kinetics in the photomechanical molecular crystal 9-methylanthracene using an extended Finke–Watzky model

In order to develop an improved description of the photomechanical response of 9-methylanthracene (9MA) microcrystals, a detailed study of its solid-state photochemical reaction kinetics is performed. The reaction progress is monitored through the decrease in absorption of an optically microcrystalline thin film. The evolution of the time-dependent photoluminescence during the reaction is also measured. Both the photochemical reaction and nonradiative relaxation rates increase as more photoproduct is formed. In order to analyze the data, an extended version of the Finke-Watzky kinetic model for photochemical reactions is derived, denoted the FW-P model. This extended version enables a systematic analysis of photochemical reaction kinetics in solid-state molecular systems at varying levels of approximation. The FW-P model describes the non-exponential decrease in reactant and also correctly predicts the magnitude of the observed decrease in photoluminescence lifetime over the course of the reaction. The lifetime analysis is complicated by the fact that the microcrystalline 9MA sample contains multiple emitting species, and the extended FW-P model fails to capture the exact dependence of the photoluminescence on product formation. Analysis of the 9MA data indicates that both the photodimerization and the nonradiative relaxation rates can be accelerated by a factor of 10 over the course of the reaction. The results in this paper demonstrate that autocatalytic photodimerization kinetics are present in crystalline 9MA and may influence its photomechanical response.

Control of Photomechanical Crystal Twisting by Illumination Direction

Photomechanical molecular crystals have been investigated as mesoscopic photoactuators. Here, we report how the photomechanical twisting of 1,2-bis(2-methyl-5-phenyl-3-thienyl)perfluorocyclopentene (1a) crystals depends on illumination direction. The ribbon-like crystal of 1a could be successfully prepared by a sublimation method. The ribbon crystal exhibited reversible photomechanical crystal twisting upon alternating irradiation with ultraviolet (UV) and visible light. Moreover, changing the UV illumination direction with respect to the crystal resulted in different twisting modes, ranging from helicoid to cylindrical. Control of photomechanical crystal deformation by illumination direction provides a convenient and useful way to generate a variety of photomechanical motions from a single crystal.

Pressure Dependence of the Forward and Backward Rates of 9-tert- Butylanthracene Dewar Isomerization

9-tert-Butylanthracene undergoes a photochemical reaction to form its strained Dewar isomer, which thermally back-reacts to reform the original molecule. When 9-tert-butylanthracene is dissolved in a polymer host, we find that both the forward and reverse isomerization rates are pressure-dependent. The forward photoreaction rate, which reflects the sum of contributions from photoperoxidation and Dewar isomerization, decreases by a factor of 1000 at high pressure (1.5 GPa). The back-reaction rate, on the other hand, increases by a factor of ∼3 at high pressure. Despite being highly strained and higher volume, the back-reaction reaction rate of the Dewar isomer is at least 100× less sensitive to pressure than that of the bi(anthracene-9,10-dimethylene) photodimer studied previously by our group. These results suggest that the high pressure sensitivity of the bi(anthracene-9,10-dimethylene) photodimer reaction is not just due to the presence of strained four-membered rings but instead relies on the unique molecular geometry of this molecule.

Photomechanically Induced Magnetic Field Response by Controlling Molecular Orientation in 9‐Methylanthracene Microcrystals

A surfactant-assisted seeded-growth method is used to form single-crystal platelets composed of 9-methylanthracene with two different internal molecular orientations. The more stable form exhibits a photoinduced twisting, as observed previously for 9-methylanthracene microribbons grown by the floating drop method. However, the newly discovered elongated hexagonal platelets undergo a photoinduced rolling-up and unrolling. The ability of the rolled-up cylindrical shape to trap superparamagnetic nanoparticles enables it to be carried along in a magnetic field gradient. The new photoinduced shape change, made possible by a novel surfactant-assisted crystal growth method, opens up the possibility of using light to modulate the crystal translational motion.

Characterization of a P-type photomechanical molecular crystal based on the E → Z photoisomerization of 9-divinylanthracene malonitrile

Anthracene derivatives with a 1,3-butadiene group attached at the 9-position can undergo E ↔ Z (trans ↔ cis) photoisomerization reactions, providing a route to new photomechanical materials. In this paper, we report the properties of a new anthracene derivative, 2-(3-anthracen-9-yl-allylidene)-malononitrile (9DVAM). The structure, photophysics and photochemistry of 9DVAM are characterized in both dilute solution and in the crystal form. This molecule possesses a strong charge-transfer transition that extends its absorption into the visible region. Photoexcitation of this transition leads to a E → Z isomerization reaction in both dilute solution and in the crystal. Rapid nonradiative relaxation and a high E → Z photoisomerization yield appear to prevent dimerization side reactions in the crystal. Exposure to ultraviolet light can partially reverse this reaction in both liquid solution and in the crystal, allowing the molecule to be cycled back and forth between its cis and trans isomers. This switching between populations can cause reversible shape changes, like bending, in crystalline microribbons and nanowires. The divinylanthracenes provide a new class of photomechanical molecular crystals that complement existing photoreversible materials.

Surfactant-Enhanced Photoisomerization and Photomechanical Response in Molecular Crystal Nanowires

Dimethyl-2(3-anthracen-9-yl)allylidene)malonate (DMAAM) is a divinylanthracene derivative that photoisomerizes between its (E) and (Z) conformations. Crystalline nanowires composed of this molecule undergo a rapid coiling motion when exposed to visible light. In this paper, a variety of experimental techniques are used to investigate the mechanism of this transformation, including powder X-ray diffraction, polarized light microscopy, 1H NMR, and absorption spectroscopy. The results show that the presence of a surfactant like cetyltrimethylammonium bromide (CTAB) accelerates the photochemical reaction rate by at least a factor of 10 within the nanowire and is required to observe the photoinduced coiling. The accelerated reaction facilitates the transition to an amorphous phase composed of reactant and photoproduct, which leads to the rapid, large-scale shape changes that the nanowires undergo. Disruption of the highly packed crystal structure by photoisomerization also enhances the dissolution rate by a factor of about 30. The fact that the nanowires have a nominal diameter of 200 nm suggests that the presence of surface species can influence the reaction dynamics deep inside the crystal. These results show that the reaction dynamics and photomechanical motions of nanoscale molecular crystals can be extremely sensitive to surface species.