Photoinduced Cascading Charge Transfer in Perylene Bisimide-Based Triads.

We synthesize three perylene bisimide-based triads with donor-acceptor-acceptor (D∼A1-A2) architectures, in which the distance between D and A1 is varied to study its influence on the excited state electron processes. Very different intramolecular charge transfer (D+∼A1-A2-) lifetimes in dichloromethane (DCM) for these three triads are revealed by steady-state and transient spectroscopies. Free-energy changes of charge transfer (CT) are calculated based on the single-crystal X-ray diffraction data and electrochemical measurements. The results show that photoinduced cascading CT comprises two competing processes in DCM (CTs in D∼A1 units and in A1-A2 units) by pumping of the A1 unit, and then the long-distance CT state is formed. The charge recombination (CR) process is restrained effectively by the increased distance between the anion and cation. This research reveals the importance of multistep cascading CTs on tuning the CT lifetime in multichromophoric systems.

Coexistence of Parallel and Rotary Stackings in the Lamellar Crystals of a Perylene Bisimide Dyad for Temperature-Sensitive Bicomponent Emission.

Coexistence of rotationally π-π stacked columns and discrete slip-stacked dimers of perylene bisimide (PBI) chromophores is revealed by single crystal X-ray diffraction in the lamellar crystal of a head-to-tail linked PBI dyad. The rotary π-π stacked columnar moieties show H-type spectral character with relatively higher excitation energy, while the discrete slip-stacked π-π dimers have J-type spectral behavior with lower excitation energy. The lamellar crystals show relatively low photoluminescence efficiency of 12% at room temperature, while this dramatically increases to ∼90% at low temperature (80 K). Both of the rotary and slip-stacked moieties are emissive, and the nonradiative energy transfer processes between them are suppressed at low temperature, ensuring the highly efficient excimer-like long-lived fluorescence.

Consecutive Charging of a Perylene Bisimide Dye by Multistep Low-Energy Solar-Light-Induced Electron Transfer Towards H2 Evolution.

A photocatalytic system containing a perylene bisimide (PBI) dye as a photosensitizer anchored to titanium dioxide (TiO2 ) nanoparticles through carboxyl groups was constructed. Under solar-light irradiation in the presence of sacrificial triethanolamine (TEOA) in neutral and basic conditions (pH 8.5), a reaction cascade is initiated in which the PBI molecule first absorbs green light, giving the formation of a stable radical anion (PBI.- ), which in a second step absorbs near-infrared light, forming a stable PBI dianion (PBI2- ). Finally, the dianion absorbs red light and injects an electron into the TiO2 nanoparticle that is coated with platinum co-catalyst for hydrogen evolution. The hydrogen evolution rates (HERs) are as high as 1216 and 1022 µmol h-1 g-1 with simulated sunlight irradiation in neutral and basic conditions, respectively.

Synthesis and Characterization of Hexapole [7]Helicene, A Circularly Twisted Chiral Nanographene.

We report the synthesis and characterization of two hexapole [7]helicenes (H7Hs). Single crystal X-ray diffraction unambiguously confirms the molecular structure. H7H absorbs light, with distinct Cotton effect, from ultraviolet to the near-infrared (λmax = 618 nm). Cyclic voltammetry reveals nine reversible redox states, consecutively from -2 to +6. These chiroptical and electronic properties of H7H are inaccessible from helicene's small homologues.

Synthesis and Characterization of Ferrocene Based Hemicages.

We present a series of tripodal ligands L1-3, which fold into hemicages C1-3 by using coordination-driven dynamic combinational chemistry. The identities of these hemicages were characterized using 1H NMR, 1H-1H COSY, DOSY, and ESI-TWIM-MS. Free rotation of the ferrocene structural units in the ligands affords an adaptable directionality, which is essential for the construction of these hemicages. Encapsulation of adamantane by C2 indicates the presence of a well-defined inner cavity as the binding pocket.

Janusarene: A Homoditopic Molecular Host.

A homoditopic molecular host, janusarene, is presented that has two back-to-back compactly arranged nanocavities for guest complexation. The unique two-face structural feature of janusarene allows it to bind and align various guest compounds concurrently, which include spherical pristine fullerene C60 and planar polycyclic aromatic hydrocarbons (PAHs), such as pyrene, perylene, and 9,10-dimethylanthracene. The host-guest interactions were characterized by single-crystal X-ray diffraction. A pairwise encapsulation of the PAH guests by janusarene enables PAH dimers to be obtained that deliver spectroscopic properties distinct from those of PAHs dissolved in solution, or in the bulk state. A monotopic control host was also synthesized and used to characterize the host-guest complexing behavior in solution.