Impact of Classical and Quantum Light on Donor-Acceptor-Donor Molecules.

Investigations of entangled and classical two-photon absorption have been carried out for six donor (D)-acceptor (A)-donor (D) compounds containing the dithieno pyrrole (DTP) unit as donor and acceptors with systematically varied electronic properties. Comparing ETPA (quantum) and TPA (classical) results reveals that the ETPA cross section decreases with increasing TPA cross section for molecules with highly off-resonant excited states for single-photon excitation. Theory (TDDFT) results are in semiquantitative agreement with this anticorrelated behavior due to the dependence of the ETPA cross section but not TPA on the two-photon excited state lifetime. The largest cross section is found for a DTP derivative that has a single photon excitation energy closest to resonance with half the two-photon excitation energy. These results are important for the possible use of quantum light for low-intensity energy-conversion applications.

D-A-D Compounds Combining Dithienopyrrole Donors and Acceptors of Increasing Electron-Withdrawing Capability: Synthesis, Spectroscopy, Electropolymerization, and Electrochromism.

Five D-π-A-π-D compounds consisting of the same donor unit (dithieno[3,2-b:2',3'-d]pyrrole, DTP), the same π-linker (2,5-thienylene), and different acceptors of increasing electron-withdrawing ability (1,3,4-thiadiazole (TD), benzo[c][1,2,5]thiadiazole (BTD), 2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione (DPP), 1,2,4,5-tetrazine (TZ), and benzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone (NDI)) were synthesized. DTP-TD, DTP-BTD, and DTP-DPP turned out to be interesting luminophores emitting either yellow (DTP-TD) or near-infrared (DTP-BTD and DTP-DPP) radiation in dichloromethane solutions. The emission bands were increasingly bathochromically shifted with increasing solvent polarity. Electrochemically determined electron affinities (|EA|s) were found to be strongly dependent on the nature of the acceptor changing from 2.86 to 3.84 eV for DTP-TD and DTP-NDI, respectively, while the ionization potential (IP) values varied only weakly. Experimental findings were strongly supported by theoretical calculations, which correctly predicted the observed solvent dependence of the emission spectra. Similarly, the calculated IP and EA values were in excellent agreement with the experiment. DTP-TD, DTP-BTD, DTP-TZ, and DTP-NDI could be electropolymerized to yield polymers of very narrow electrochemical band gap and characterized by redox states differing in color coordinates and lightness. Poly(DTP-NDI) and poly(DTP-TD) showed promising electrochromic behavior, not only providing a rich color palette in the visible but also exhibiting near-infrared (NIR) electrochromism.

Direct Reductive Cyclocondensation of the Nitro Group with the Amido Group: Key Role of the Iminophosphorane Intermediate in the Synthesis of 1,4-Dibenzodiazepine Derivatives.

A class of dialkylamino-substituted dibenzodiazepines and their hetero analogues was synthesized by the intramolecular aza-Wittig condensation of the amido group with iminophosphoranes. The one-pot, two-step procedure includes reductive synthesis of the intermediate iminophosphoranes from the corresponding nitroamides and tributylphosphine.