Direct observation of electron transfer in solids through X-ray crystallography.

Nanoscale electron transfer (ET) in solids is fundamental to the design of multifunctional nanomaterials, yet its process is not fully understood. Herein, through X-ray crystallography, we directly observe solid-state ET via a crystal-to-crystal process. We first demonstrate the creation of a robust and flexible electron acceptor/acceptor (A/A) double-wall nanotube crystal ([(Zn)(L)(L)]) with a large window (0.

Rapid Synthesis of Chiral Figure-Eight Macrocycles Using a Preorganized Natural Product-Based Scaffold.

Chiral D -symmetric figure-eight shaped macrocycles are promising scaffolds for amplifying the chiroptical properties of π-conjugated systems. By harnessing the inherent and adaptable conformational dynamics of a chiral C -symmetric bispyrrolidinoindoline (BPI) manifold, we developed an enantio-divergent modular synthetic platform to rapidly generate a diverse range of chiral macrocycles, spanning from 14- to 66-membered rings, eliminating the need for optical resolution. Notably, a 32-membered figure-eight macrocycle showed excellent circularly polarized luminescence (CPL: |g |=1.

Optical Resolution of Carboxylic Acid Derivatives of Homoleptic Cyclometalated Iridium(III) Complexes via Diastereomers Formed with Chiral Auxiliaries.

We report on a facile method for the optical resolution of cyclometalated iridium(III) (Ir(III)) complexes via diastereomers formed with chiral auxiliaries. The racemic carboxylic acids of Ir(III) complexes (- (-Ir(ppyCOH) (ppy: 2-phenylpyridine)), - (-Ir(tpyCOH) (tpy: 2-(4'-tolyl)pyridine)), and - (-Ir(mpiqCOH) (mpiq: 1-(4'-methylphenyl)isoquinoline))) were converted into the diastereomers, Δ- and Λ-forms of - (from -), - (from -), - (from -), and - (from -), respectively, by the condensation with (12)-1,2-diaminocyclohexane or (12)-2-aminocyclohexanol. The resulting diastereomers were separated by HPLC (with a nonchiral column) or silica gel column chromatography, and their absolute stereochemistry was determined by X-ray single-crystal structure analysis and CD (circular dichroism) spectra.

Catalytic electron drives host-guest recognition.

Electron injection is demonstrated to trigger electrocatalytic chain reactions capable of releasing a solvent molecule and forming a redox active guest molecule. One-electron reduction of a hydroxy anthrone derivative (AQH-CHCN) results in the formation of an anthraquinone radical anion (AQ˙) and acetonitrile (CHCN). The resulting fragment of AQ˙ exhibits high stability under mild reducing conditions, and it has enough reducing power to reduce the reactant of AQH-CHCN.

Zinc-Ion-Stabilized Charge-Transfer Interactions Drive Self-Complementary or Complementary Molecular Recognition.

Here, we show that charge-transfer interactions determine whether donor and acceptor ditopic ligands will associate in a complementary or self-complementary fashion upon metal-ion clipping. Anthracene-based ( and ) and anthraquinone-based () ditopic ligands containing two imidazole side arms as zinc coordination sites were designed. The and systems associated in a complementary fashion (//) upon clipping by two zinc ions (Zn) to form an alternating donor-acceptor assembly [()()-(Zn)].

Remarkable self-sorting selectivity in covalently linked homochiral and heterochiral pairs driven by PdL helicate formation.

Imidazole-based ditopic ligands bearing two chiral alkyl groups (LRR, LSS, and LRS) were synthesized. The ligands formed Pd2L4 helicates with palladium ions (Pd2+). Self-sorting occurred between LRR and LRS to form (Pd2+)2(LRR)4 and (Pd2+)2(LRS)4 homoligand assemblies, whereas mixing of LRR and LSS with Pd2+ gave a near statistical mixture.

Dynamic Open Coordination Cage from Nonsymmetrical Imidazole-Pyridine Ditopic Ligands for Turn-On/Off Anion Binding.

This work demonstrates a new nonconventional ligand design, imidazole/pyridine-based nonsymmetrical ditopic ligands (1 and 1 ), to construct a dynamic open coordination cage from nonsymmetrical building blocks. Upon complex formation with Pd at a 1:4 molar ratio, 1 and 1 initially form mononuclear PdL complexes (Pd (1) and Pd (1 ) ) without formation of a cage. The PdL complexes undergo a stoichiometrically controlled structural transition to Pd L open cages ((Pd ) (1) and (Pd ) (1 ) ) capable of anion binding, leading to turn-on anion binding.