Unique Type II Halogen···Halogen Interactions in Pentafluorophenyl-Appended 2,2′-Bithiazoles

Herein, we report the design and synthesis of 2,2′-bithiazole derivatives with efficient intermolecular halogen interactions. The single crystal X-ray diffraction studies revealed unique type-II halogen interactions in these derivatives. The shortest type-II F···F interactions within the distance of 2.67 Å, at an angle of 89.1° and 174.2°, was observed for the first time. The Gaussian calculations were performed to further establish predominant F···F interactions

Modulation of Electronic and Self-Assembly Properties of a Donor–Acceptor–Donor-Based Molecular Materials via Atomistic Approach

The performance of molecular materials in optoelectronic devices critically depends upon their electronic properties and solid-state structure. In this report, we have synthesized sulfur and selenium based (<b>T4BT</b> and <b>T4BSe</b>) donor–acceptor–donor (D–A–D) organic derivatives in order to understand the structure–property correlation in organic semiconductors by selectively tuning the chalcogen atom. The photophysical properties exhibit a significant alteration upon varying a single atom in the molecular structure. A joint theoretical and experimental investigation suggests that replacing sulfur with selenium significantly reduces the band gap and molar absorption coefficient because of lower electronegativity and ionization potential of selenium. Single-crystal X-ray diffraction analysis showed differences in their solid-state packing and intermolecular interactions. Subsequently, difference in the solid-state packing results variation in self-assembly. Micorstructural changes within these materials are correlated to their electrical resistance variation, investigated by conducting probe atomic force microscopy (<b>CP-AFM</b>) measurements. These results provide useful guidelines to understand the fundamental properties of D–A–D materials prepared by atomistic modulation

Unique Type II Halogen···Halogen Interactions in Pentafluorophenyl-Appended 2,2′-Bithiazoles

Herein, we report the design and synthesis of 2,2′-bithiazole derivatives with efficient intermolecular halogen interactions. The single crystal X-ray diffraction studies revealed unique type-II halogen interactions in these derivatives. The shortest type-II F···F interactions within the distance of 2.67 Å, at an angle of 89.1° and 174.2°, was observed for the first time. The Gaussian calculations were performed to further establish predominant F···F interactions

Reversible Photolysis of Nitrosobenzene <i>cis</i>-Dimer Monitored In Situ by Single Crystal Photocrystallography

A single crystal of the <i>cis</i>-dimer of nitrosobenzene was directly observed by photocrystallography to transition to a pair of monomers and reversibly redimerize. The remarkable displacement of the nitrogen atoms within the crystalmoving a total distance of 2.97(5) Å for the two atomssuggests that the breadth of solid-state photochemical reaction systems susceptible to X-ray diffraction studies need not be limited to those with very small atomic displacements

Reversible Photolysis of Nitrosobenzene <i>cis</i>-Dimer Monitored In Situ by Single Crystal Photocrystallography

A single crystal of the <i>cis</i>-dimer of nitrosobenzene was directly observed by photocrystallography to transition to a pair of monomers and reversibly redimerize. The remarkable displacement of the nitrogen atoms within the crystalmoving a total distance of 2.97(5) Å for the two atomssuggests that the breadth of solid-state photochemical reaction systems susceptible to X-ray diffraction studies need not be limited to those with very small atomic displacements