Search

[2]Rotaxanes offer unique opportunities for studying and modulating charge separation and energy transfer, because the mechanical bond allows the robust, yet spatially dynamic tethering of photoactive groups. In this work, we synthesized [2]rotaxane triads comprising a central (aza)[10]CPP⊃C60 bis‐adduct complex and two zinc porphyrin stoppers to address how the movable nanohoop affects light‐induced charge separation and energy transfer between the rotaxane subcomponents. We found that neither the parent nanohoop [10]CPP nor its electron‐deficient analogue aza[10]CPP actively participate in charge separation. In contrast, the nanohoops completely prevented through‐space charge separation. This result is likely due to supramolecular "shielding", because charge separation was observed in the thread that acted as reference dyad. On the other hand, the suppression of electron transfer allowed the observation of energy transfer from the porphyrin triplet to the fullerene triplet state with a lifetime of ca. 25 μs. The presence of the interlocked nanohoops therefore leads to a dramatic switch between charge separation and energy transfer. We suggest that our results explain observations made by others in photovoltaic devices comprising nanohoops and may pave the way toward strategic uses of mechanically interlocked architectures in devices that feature (triplet) energy transfer. [ABSTRACT FROM AUTHOR]

The mechanism of visible light-induced hole transfer from a molecular light absorber, in the form of a free-base porphyrin, coupled to a Co3O4 nanoparticle catalyst for water oxidation by a molecular wire (p-oligo(phenylenevinylene) featuring three aryl units) is investigated by transient absorption spectroscopy. The wires are covalently anchored on the Co3O4 surface and embedded in a dense, yet ultrathin (2 nm), silica layer that separates light absorber and catalyst. The porphyrin is electrostatically adsorbed on the silica surface, and aqueous colloidal solutions of the core-shell particles are used for transient optical measurements. Pulsed optical excitation of the porphyrin results in rapid injection of the photogenerated hole onto the molecular wire and concurrent formation of reduced light absorber in less than 1 picosecond (ps). Ultrafast charge separation was monitored by transient absorption of the wire radical cation, which is given by bands in the 500 to 600 nm region and at 1130 nm, while formation of reduced porphyrin was characterized by absorption at 700 nm. Forward transfer of the hole to Co3O4 catalyst proceeds in 255 ± 23 ps. Ultrafast transfer of positive charge from the molecular assembly to a metal oxide nanoparticle catalyst for water oxidation is unprecedented. Holes on Co3O4 recombined with electrons of the reduced sensitizer with biphasic kinetics on a much longer time scale of ten to several hundred nanoseconds. The unusually efficient hole transfer coupling of a molecular light absorber with an Earth-abundant metal oxide catalyst by silica-embedded p-oligo(phenylenevinylene) offers an approach for integrated artificial photosystems featuring product separation on the nanoscale.

A new clear‐cut strategy for fusing N‐heterocyclic and carbon‐pure systems is introduced en route to a versatile platform of multi‐purpose tetrapyrrolic chromophores. In particular, three novel C−C bond‐fused porphyrin‐hexabenzocoronene (HBC) conjugates were synthesized under oxidative cyclodehydrogenation conditions, starting from tailor‐made nickel porphyrin precursors. The fusion of the individual aromatic systems via 5‐membered rings led to highly soluble π‐extended porphyrins in excellent yields. The resulting porphyrin‐HBC conjugates exhibit absorption cross‐sections that are of interdisciplinary interest in the ever‐growing field of organic photovoltaics and near‐infrared (NIR) dyes. Quantum chemical calculations show that the newly formed 5‐membered rings induce biradicaloid character in the porphyrin core, which has a strong impact on excited state lifetimes. This is confirmed by a thorough optoelectronic and time‐resolved characterization in order to understand these unique features better. Broadened absorption characteristics go hand‐in‐hand with short‐lived excited states with up to six orders of magnitude faster decay rates. [ABSTRACT FROM AUTHOR]

In tetracene, the energies of the lowest singlet excited state and twice that of the lowest triplet excited state are similar, allowing both down‐conversion (i.e., singlet fission, SF) and up‐conversion (i.e., triplet‐triplet annihilation up‐conversion, TTA‐UC) processes. Through‐space and through‐bond contributions to the inter‐tetracene coupling in purposefully designed oligomers play a crucial role in determining which of the two processes dominates. In this work, the focus is exclusively on SF in newly synthesized oligo‐tetracenes linked by conjugated [2.2]paracyclophane (PCP) building blocks. By choosing different PCP substitution patterns and by varying the degree of substitution the inter‐tetracene couplings are addressed. An independent variable is connecting the tetracences to the PCP at different positions to alter the through‐bond and through‐space coupling of the resulting oligo‐tetracenes. The novel oligo‐tetracenes are investigated by means of steady‐state and time‐resolved absorption and fluorescence spectroscopies with respect to the initial events of SF, that is, the transformation of a singlet excited state into a correlated triplet pair state. Briefly, through‐space couplings are profoundly weaker than through‐bond couplings that enable the correlated triplet pair state formation. If interactions are through‐space, correlated triplet pair state formation is turned off, while it is turned on if through‐bond interactions are operative. [ABSTRACT FROM AUTHOR]

Chiral carbon nanodots (CNDs) were fabricated through the hydrothermal processing of sulfanilic acid and chiral tartaric acid, exhibiting outstanding catalytic performance for the chiral catalysis of the ring-opening reaction. Furthermore, the catalytic mechanism was proposed to understand the link between the chiral structure and the performance of the catalyst. [ABSTRACT FROM AUTHOR]