Conjugation Extension and Halochromic Behaviors of S-Fused Polycyclic Aromatic Hydrocarbons Bearing Cyclopenta[b]thiopyran Moieties.

Three S-fused polycyclic aromatic hydrocarbons (PAHs) bearing cyclopenta[b]thiopyran moieties have been designed and successfully synthesized. With the conjugation extension, the absorption onset of the longest PAH reaches 1110 nm. All the three S-fused PAHs exhibit significant halochromic properties in both solution and solid states. Upon protonation, the proton is incorporated on the cyclopentadiene ring while the positive charge is localized on the thiopyrylium ring. Moreover, no significant difference can be found for the two shorter PAHs upon the protonation by different organic acids, such as trifluoroacetic acid (TFA) and trifluoromethanesulfonic acid (TfOH), while the longest PAH can be only mono-protonated by TFA but di-protonated by stronger TfOH. Furthermore, after protonation, the non-emissive S-fused PAHs exhibit strong fluorescence and can be regenerated by simply neutralization with triethylamine. The enhanced emission of mono-protonated products stem from S2 →S0 transitions, which disobey the Kasha's rule.

Synthesis of silica-stabilized Ag44 clusters aided by a designed mercaptosilane ligand.

The novel and precise design of both a microscopic ligand and macroscopic structure has been demonstrated to improve the stability and potential optical applications of Ag44 clusters. The ligand with designed silane substituents on its thiophenol enabled the synthesized [Ag44(SPhSi(OEt)3)30](PPh4)4 clusters to maintain UV-vis absorption for 13 h when heated at 60 °C in air and be readily coated with silica shells via a one-pot reverse microemulsion method. This composite structure overcomes the issue that non-luminescent Ag44 clusters cannot be applied in photothermal and photoacoustic imaging due to their instability.