Hierarchically Organized Cocrystal of Tetra-Anionic Porphyrin and Di-Cationic Viologen: Ion Conformations, Supramolecule Interactions, and Porphyrin Arrays.

Ionic co-assembly of tetra-anionic porphyrins has been extensively researched in the construction of hierarchically organized architectures with potential application value in organic semiconductors, sunlight catalysts and supramolecular chirality systems. However, such architectures are difficult to grow to a size suitable for single-crystal X-ray diffraction (SCXRD); the lack of single-crystal structures of these architectures leads to challenges in gaining deeper comprehension about that. This study reports a hierarchically organized cocrystal of meso-tetra(4-sulfonato-phenyl)-porphyrin (TSPP4- ) and N, N'-diethyl-viologen (DEV2+ ), wherein wave-like and saddle-like TSPP4- ions co-aggregate at a stoichiometric ratio of 1 : 2 to form unique porphyrin arrays; the spectrum characteristics and calculated coulombic exciton coupling energy show that these porphyrin arrays are J-aggregates. We prove that the distortion of porphyrin ring of TSPP4- strongly correlates with the deflection of its phenyl groups. The crystal comprises six different ionic conformations, and the multiplicity of ionic conformation leads to intricate supramolecular interactions.

Insights into the Self-Assembly of a Heterocluster Janus Molecule into Colloidal Onions.

Diverse nanostructures and nano-objects for advanced applications are created by the self-assembly of lipids, surfactants, and block copolymers. Understanding this process is critical for improving their functions and expanding their applications. Accordingly, we pioneered the synthesis and application of heterocluster Janus molecules (HCJMs), which resemble conventional amphiphiles. Their self-assembly into nanostructures and nano-objects can be directly characterized by transmission electron microscopy (TEM), allowing the process to be unraveled through the monitoring of the intermediates. In this study, we focused on the TEM characterization of HCJM-based colloidal onions, which have an onion-like inner structure, to gain insight into the self-assembly process from molecules to perfect onions. Multiple mechanisms, including molecular aggregation, structural ordering within aggregates into colloidal onions, and layer-by-layer growth caused by particle coarsening, contributed to the overall self-assembly process. The analysis also indicated that the reduction in the Gibbs free energy and bending free energy of curved layers are the driving forces for structural ordering and onion growth. Finally, this work provided a useful method for preparing colloidal onions for attractive applications in nanomedicine and other areas.

Highly Efficient Multicolor-Emitting Tetraphenylethylene-Based Organic Salts with Commercialization Prospects.

Since the discovery of aggregation-induced emission from tetraphenylethylene derivatives, various methods have been explored to prepare highly efficient multicolored luminescent materials. Herein, we report a simple and efficient strategy for constructing luminescent organic salts of the tetracationic luminogen, tetrapyridinium-tetraphenylethylene (T4Py-TPE4+), combined with seven di- and tetra-anionic aromatic sulfonate ligands. When aqueous solutions of the cationic luminogen and the anionic ligands were mixed, they rapidly aggregated into organic salts within seconds to minutes, giving yields of up to >90%. This was accompanied by an increase in the emission efficiency from ∼58% to almost 100%, and the ability to tune the emission color between 511 and 586 nm. These improvements were mainly attributed to the strong electrostatic attractions between the cation and anions, which resulted in the formation of a rigid hydrophobic network of the T4Py-TPE4+ luminogen with various π-conjugation lengths. Because these compounds are commercially available, this method opens the possibility of fabricating novel light-emitting materials for device fabrication and research.

Synthetic and structural studies on new diiron azadithiolate (ADT)-type model compounds for active site of [FeFe]hydrogenases.

A series of new diiron azadithiolate (ADT) complexes (1-8), which could be regarded as the active site models of [FeFe]hydrogenases, have been synthesized starting from parent complex [(µ-SCH(2))(2)NCH(2)CH(2)OH]Fe(2)(CO)(6) (A). Treatment of A with ethyl malonyl chloride or malonyl dichloride in the presence of pyridine afforded the malonyl-containing complexes [(µ-SCH(2))(2)NCH(2)CH(2)O(2)CCH(2)CO(2)Et]Fe(2)(CO)(6) (1) and [Fe(2)(CO)(6)(µ-SCH(2))(2)NCH(2)CH(2)O(2)C](2)CH(2) (2). Further treatment of 1 and 2 with PPh(3) under different conditions produced the PPh(3)-substituted complexes [(µ-SCH(2))(2)NCH(2)CH(2)O(2)CCH(2)CO(2)Et]Fe(2)(CO)(5)(PPh(3)) (3), [(µ-SCH(2))(2)NCH(2)CH(2)O(2)CCH(2)CO(2)Et]Fe(2)(CO)(4)(PPh(3))(2) (4), and [Fe(2)(CO)(5)(PPh(3))(µ-SCH(2))(2)NCH(2)CH(2)O(2)C](2)CH(2) (5). More interestingly, complexes 1-3 could react with C(60) in the presence of CBr(4) and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) via Bingel-Hirsch reaction to give the C(60)-containing complexes [(µ-SCH(2))(2)NCH(2)CH(2)O(2)CC(C(60))CO(2)Et]Fe(2)(CO)(6) (6), [Fe(2)(CO)(6)(µ-SCH(2))(2)NCH(2)CH(2)O(2)C](2)C(C(60)) (7), and [(µ-SCH(2))(2)NCH(2)CH(2)O(2)CC(C(60))CO(2)Et]Fe(2)(CO)(5)(PPh(3)) (8). The new ADT-type models 1-8 were characterized by elemental analysis and spectroscopy, whereas 2-4 were further studied by X-ray crystallography and 6-8 investigated in detail by DFT methods.