Photoactive Organic/Inorganic Hybrid Materials with Nanosegregated Donor–Acceptor Arrays

Abstract

The synthesis of the first mesogenic donor-acceptor polyoxometalate (POM)-based hybrid is herein described. The structural and electronic properties of the hybrid compound were evaluated through combination of small-and wide-angle X-ray scattering, optical microscopy, electrochemistry and photoluminescence. In the solid state, the compound behaves as a birefringent solid, displaying a lamellar organization in which double-layers of POMs and bis(thiophene)thienothiophene organic donors alternate regularly. Noticeably, the subunit organizations in the composite are similar to that observed for the individual POM and organic donor precursors. Photophysical studies show that in the hybrid, the fluorescence of the organic donor unit is considerably quenched both in solution and in the solid state, which is attributed to occurrence of intramolecular charge-separated state.

The precise modification of a nanoscaled Keplerate-type polyoxometalate with NH2-groups: reactive sites, mechanisms and dye conjugation

“…In addition, three-coordinated μ 3 -O appears after APTMS binds; however, such behavior was not observed for oxygens in lacunary PW 11 Keggin and Dawson with grafted alkoxysilane. 37,38…”

“…In addition, three-coordinated μ 3 -O appears after APTMS binds; however, such behavior was not observed for oxygens in lacunary PW 11 Keggin and Dawson with grafted alkoxysilane. 37,38 Finally, one more possibility for APTMS grafting should be discussed. Based on the bond length 2.34 Å between molybdenum and oxygen from acetic acid inside the Keplerate cavity, these oxygens can also react with APTMS.…”