W Tungsten

Two families of dyad and triad systems based on perylene monoimide (PMI), quaterthiophene (QT), and 9,10-bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene (extended tetrathiafulvalene, exTTF) molecular components deceive been designed and synthesized. The dyads (D1 and D2) are of the PMI-QT epitome and the triads (T1 and T2) of the PMI-QT-exTTF transcribe. The two families part company in the saturated or unsaturated stamp of the linker groups (ethynylene in D1 and T1, ethylene in D2 and T2) that unite the molecular components. The dyads and triads be dressed been characterized by electrochemical, photophysical, and computational methods. Both the experiential and the computational (DFT) results indicate that in the unsaturated systems efficacious intercomponent interactions advantage to substantial perturbation of the properties of the subunits. In particular, in T1, delocalization is outstandingly functional internuncio the QT and ExTTF units, which would be bettor viewed combined as a single electronic subsystem. For the dyad systems, the photophysics observed following excitation of the PMI segment is solvent-dependent. In somewhat Siberian solvents (dichloromethane, diethyl ether) soundly charge separation is followed by recombination to the deposit governmental. In toluene, dilatory conversion to the charge-separated conditions is followed by intersystem crossing and recombination to yield the triplet phase of the PMI module. The behavior of the triads, on the other hand, is remarkably like to that of the corresponding dyads, which indicates that, after zenith charge separation, hole shift from the oxidized QT component to ExTTF is altogether inefficient. This unexpected result has been rationalized on the essence of the anomalous (simultaneous two-electron oxidation) electrochemistry of ExTTF and with the boost of DFT calculations. In fact, although ExTTF is electrochemically easier to oxidize than QT by around 0.6 V, the one-electron redox orbitals (HOMOs) of the two units in triad T2 are almost go to the dogs <<>>