The energy-transfer properties of a regioregular silylene-spaced alternating donor−acceptor copolymer (donor−SiMe2−acceptor−SiMe2) m are determined with time-resolved spectroscopy; 4,4′-divinylbiphenyl serves as donor and 4,4′-divinylstilbene as acceptor. Steady-state fluorescence spectra show that the energy transfer is efficient. With excitation at 266 nm, fluorescence up-conversion curves at various detection wavelengths are measured to explore the detailed dynamics of the energy transfer. A rate ∼(0.3 ps)−1 for energy transfer between the S1 states of the donor and acceptor moieties is observed. Theoretical calculations based on fragment excitation difference provide a rate of energy transfer near the experimental value with detailed insight into the mechanism of energy transfer. The results of theoretical calculations indicate that the Coulomb interaction is dominant and the Dexter process is weak. The high-multipole interactions are important for energy transfer.
Supramolecular assembly of donor-acceptor complexes as the key component in organic functional nanomaterials is a promising approach for future electronic devices. One representative example of the donor-acceptor complexes is the naphthalene diimide-pyrene (NDI-Py) system, which shows fascinating photoelectric properties. Herein, the analysis of the π-π interactions between NDI and Py has been investigated using the DFT/M06-2X and reduced density gradient methods. According to the calculations, the attractive forces for the stabilization of the NDI-Py dimer are dependent on the rotation angles, which provide physical insight into the experimental data reported by Wilson and co-workers (Langmuir, 2011, 27, 6554). Our results not only provide computational evidence for the origin of the rotation in the crystal structure of the NDI-Py but also address the role of the charge-transfer attractions in the complexes.
Herein, we report a tetraphenylethylene-diglycine (TPE-GG) hydrogelator from a systematic study of TPE-capped dipeptides with various amphiphilic properties. From a chemical design, we found that the hydrogelation of TPE-GG molecules can be utilized to generate supramolecular nanostructures with a large TPE-based nanobelt width (∼300 nm) and lateral dimension ratio (>30 fold). In addition, TPE-GG has the lowest molecular weight and minimum number of atoms compared to any TPE-capped peptide hydrogelator reported to date. This minimal self-assembled hydrogelator can fundamentally achieve the gel features compared with other TPE-capped peptides. A combined experimental and computational study indicates the π-π interactions, electrostatic interactions and hydrogen-bonding interactions are the major driving forces behind the formation of self-assembled nanobelts. This study demonstrates the importance of structure-property relationships and provides new insights into the design of supramolecular nanomaterials.
The relaxation dynamics of excited electronic states of [(1,1'-biphenyl)-4,4'-diyldi-2,1-ethenediyl]bis(dimethylsilane) dissolved in various solvents with varied polarity and viscosity have been investigated. Upon excitation at wavelength 266 nm, we measured the fluorescence curves that exhibit a rise time constant approximately 100 fs, and two decay time constants, 7-65 ps and approximately 1 ns. We attribute the former decay to upper excited states to the S(1) state, and the latter decay to geometric relaxation and the lifetime of the S(1) state. Only the tens of picosecond decay shows a dependence on the solvent viscosity, indicating that the torsional motion dominates the relaxation. Theoretical calculations were performed to obtain the optimized structures of the free [(1,1'-biphenyl)-4,4'-diyldi-2,1-ethenediyl]bis(dimethylsilane) molecule in its ground and first excited states with methods B3LYP/6-311G(d) and CIS/6-311G(d), respectively. The results of these calculations show that the dihedral angle between the two phenyl rings is approximately 34 degrees for trans and approximately 38 degrees for cis conformers in the ground state and that the first excited state has a planar structure, in agreement with the experimental results that indicate that the torsional motion of two phenyl groups elevates the relaxation of the S(1) state. Enhanced vibrational relaxation of S(1) in alcoholic solvents is observed. Rapid relaxation in methanol-OH compared with that in methanol-OD is explained by the excess energy dissipated efficiently through high-frequency vibrational mode (>500 cm(-1)).
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