Design and theoretical study of D-A- π -A organic sensitizers with [1,2,5]Thiadiazolo[3,4- c ]pyridine, [1,2,5]Selenadiazolo[3,4- c ]pyridine, and [1,2,5]Oxadiazolo[3,4- c ]pyridine π Component

The study concerns molecular design and theoretical study of novel prospective organic sensitizers based on D–A–π–A concept. A modification of the concept (DA–π–A) and new ways for design of organic sensitizers are proposed. The study shows thatπ-block plays a key role for the wavelength shift in UV-Vis spectra. An existence of element of higher periods in theπ-block provides a noticeable bathochromic shift. The thienyl bridge in A-block provides a red shift with respect to phenyl bridge for[1,2,5]oxadiazolo[3,4-c]pyridines while the phenyl bridge provides a red shift with respect to thienyl bridge for[1,2,5]selenadiazolo[3,4-c]pyridines. The maximal wavelengths are observed for DA-blocks with aliphatic/alicyclic fragments we proposed. An influence of enthalpy of formation and polarity of DA-blocks on bathochromic shift is shown. The quantitative dependencies of wavelengths on the enthalpies and dipole moments are determined. The maximal oscillator strengths are observed for the planar DA-block. Therefore, the conditions for design of compounds possessing the maximal wavelengths and oscillator strengths are different: the latter presupposes the planar structure of DA-block while the first presupposes an existence of nonplanar aliphatic/alicyclic fragments. Thus, the further design of organic sensitizers should include some combination of these concepts.