Excited-State Charge Transfer in Covalently Functionalized MoS2 with a Zinc Phthalocyanine Donor-Acceptor Hybrid.

The functionalization of MoS2 is of paramount importance for tailoring its properties towards optoelectronic applications and unlocking its full potential. Zinc phthalocyanine (ZnPc) carrying an 1,2-dithiolane oxide linker was used to functionalize MoS2 at defect sites located at the edges. The structure of ZnPc-MoS2 was fully assessed by complementary spectroscopic, thermal, and microscopy imaging techniques. An energy-level diagram visualizing different photochemical events in ZnPc-MoS2 was established and revealed a bidirectional electron transfer leading to a charge separated state ZnPc.+ -MoS2 .- . Markedly, evidence of the charge transfer in the hybrid material was demonstrated using fluorescence spectroelectrochemistry. Systematic studies performed by femtosecond transient absorption revealed the involvement of excitons generated in MoS2 in promoting the charge transfer, while the transfer was also possible when ZnPc was excited, signifying their potential in light-energy-harvesting devices.

Solvent-dependent photo-induced dynamics in a non-rigidly linked zinc phthalocyanine-perylenediimide dyad probed using ultrafast spectroscopy.

In this work, we characterize the energy and electron transfer kinetics of a zinc phthalocyanine-perylenediimide dyad (ZnPc-PDI) in various solvents using steady-state and tunable narrowband pump-probe spectroscopy. We fit the ultrafast data with global analysis techniques and find that upon excitation of the PDI moiety (pump pulse at 540 nm), the excitation energy transfer (EET) rate to the ZnPc moiety displays a solvent sensitivity that we attribute to changes in the relative equilibrium moiety orientation. We rationalize these observations by considering the nature of the non-rigid bridge used to link the two moieties as well as the degenerate nature of the Q band transitions in the ZnPc species. By tuning the pulse into resonance with the ZnPc Q band (685 nm) we can directly photo-induce an electron transfer (ET) process back to the PDI moiety. Employing the same global analysis, we find that the dynamics of the ultrafast electron transfer are completely kinetically controlled according to the Bixon-Jortner model of barrierless solvent-controlled curve crossing, while the recombination to reform the ground state is well-described using the static energetic picture according to Marcus theory.

Phthalocyanine-Gold Nanoparticle Hybrids: Modulating Quenching with a Silica Matrix Shell.

An asymmetrically substituted zinc phthalocyanine (ZnPc) with a terminal dithiolane group is anchored to Au nanoparticles (NPs) directly or through an interposed silica matrix. Transient absorption spectroscopy shows that the quenching of the ZnPc excited state by AuNPs occurs through a photoinduced electron transfer, the efficiency of which is modulated by the presence of the insulating silica matrix.

Large-Size Star-Shaped Conjugated (Fused) Triphthalocyaninehexaazatriphenylene.

Star-shaped triphthalocyaninehexaazatriphenylene 1 was synthesized via condensation between a new building block 1,2-diaminophthalocyanine and cyclohexanehexaone. Compound 1 represents the largest star-shaped phthalocyanine-fused hexaazatriphenylene reported so far. This largely expanded phthalocyanine shows good solubility and has a strong tendency to aggregate both in solution and on the surface, indicating its potential as an active component in organic electronic devices.

Direct Hydrogen Evolution from Saline Water Reduction at Neutral pH using Organic Photocathodes.

Here, we have developed an organic photocathode for water reduction to H2 , delivering more than 1 mA cm-2 at 0 V versus RHE and above 3 mA cm-2 at -0.5 V versus RHE with moderate stability under neutral pH conditions. The initial competitive reduction of water to H2 and ZnO to metallic Zn is responsible for the dynamic behaviour of both photocurrent and Faradaic efficiency of the device, which reaches 100 % Faradaic efficiency after 90 min operation. In any case, outstanding stable H2 flow of approximately 2 µmol h-1 is measured over 1 h at 0 V versus RHE and at neutral pH, after equilibrium between the Zn2+ /Zn0 concentration in the AZO film is reached. This achievement opens new avenues for the development of allsolution-processed organic photoelectrochemical cells for the solar generation of H2 from sea water.

Efficient passivated phthalocyanine-quantum dot solar cells.

The power conversion efficiency of CdSe and CdS quantum dot sensitized solar cells is enhanced by passivation with asymmetrically substituted phthalocyanines. The introduction of the phthalocyanine dye increases the efficiency up to 45% for CdSe and 104% for CdS. The main mechanism causing this improvement is the quantum dot passivation. This study highlights the possibilities of a new generation of dyes designed to be directly linked to QDs instead of the TiO2 electrodes.

Rational design of a phthalocyanine-perylenediimide dyad with a long-lived charge-separated state.

A new ZnPc-PDI dyad presenting for the first time a charge-separated state lower in energy than the triplet excited state of the ZnPc and PDI has been synthesized. The rational design implies the substitution of the ZnPc with phenoxy groups and the bay substitution of the PDI with sulfonyl substituents. The lifetime of the charge-separated state was 72 µs.