Synthesis of D-π-A'-π-A Chromophores with Quinoxaline Core as Auxiliary Acceptor and Effect of Various Silicon-Substituted Donor Moieties on Thermal and Nonlinear Optical Properties at Molecular and Material Level.

Novel D-π-A'-π-A chromophores with quinoxaline cores as auxiliary acceptors and various donor moieties (aniline, carbazole, phenothiazine, tetrahydroquinoline) containing bulky -butyldimethylsilyloxy (TBDMSO) groups and tricyanofuranyl (TCF) acceptors with bulky cyclohexylphenyl substituents were synthesized via eight- to nine-step procedures, and their photo-physical and thermal properties were investigated. The values of the chromophores' first hyperpolarizabilities were calculated in the framework of DFT at the M06-2X/aug-cc-pVDZ computational level; the effect of the introduction of the TBDMSO group into the donor fragment is shown to be inessential, as this group is not coupled to the π-conjugated system of the chromophore. The chromophore with the tetrahydroquinoline donor has a first hyperpolarizability value of 937 × 10 esu, which is the highest for the studied chromophores.

Deep-Blue Emissive Copper(I) Complexes Based on P-Thiophenylethyl-Substituted Cyclic Bisphosphines Displaying Photoinduced Structural Transformations of the Excited States.

A synthetic method for a primary 2-(thiophen-2'-yl)ethylphosphine was developed. The reaction of thiophenylethylphosphine with paraformaldehyde and primary arylamines leads to the formation of cyclic bisphosphines, namely, 1,5-di(aryl)-3,7-bis(thiophenylethyl)-1,5-diaza-3,7-diphosphacyclooctane (aryl = phenyl, -tolyl). The obtained bisphosphines form cationic bis-P,P-chelate complexes with copper(I) tetrafluoroborate, which were structurally characterized by NMR spectroscopy, mass spectrometry, and elemental and XRD analyses.