Fused Hexabenzocoronene-Porphyrin Conjugates with Tailorable Excited-State Lifetimes.

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.

Understanding the Visible Absorption of Electron Accepting and Donating CNDs.

Carbon nanodots (CNDs) synthesized from citric acid and formyl derivatives, that is, formamide, urea, or N-methylformamide, stand out through their broad-range visible-light absorbance and extraordinary photostability. Despite their potential, their use has thus far been limited to imaging research. This work has now investigated the link between CNDs' photochemical properties and their chemical structure. Electron-rich, yellow carbon nanodots (yCNDs) are obtained with in situ addition of NaOH during the synthesis, whereas otherwise electron-poor, red carbon nanodots (rCNDs) are obtained. These properties originate from the reduced and oxidized dimer of citrazinic acid within the matrix of yCNDs and rCNDs, respectively. Remarkably, yCNDs deposited on TiO2 give a 30% higher photocurrent density of 0.7 mA cm-2 at +0.3 V versus Ag/AgCl under Xe-lamp irradiation (450 nm long-pass filter, 100 mW cm-2 ) than rCNDs. The difference in overall photoelectric performance is due to fundamentally different charge-transfer mechanisms. These depend on either the electron-accepting or the electron-donating nature of the CNDs, as is evident from photoelectrochemical tests with TiO2 and NiO and time-resolved spectroscopic measurements.

Non-Covalent Postfunctionalization of Dye Layers on TiO2 - A Tool for Enhancing Injection in Dye-Sensitized Solar Cells.

We report on newly tailored dye layers, which were employed, on one hand, for covalent deposition and, on the other hand, for non-covalently post-functionalizing TiO2 nanoparticle films. Our functionalization concept enabled intermixing a stable covalent attachment of a first layer with a highly versatile and reversible hydrogen bonding through the Hamilton receptor-cyanuric acid binding motif as a second layer. Following this concept, we integrated step-by-step a first porphyrin layer and a second porphyrin/BODIPY layer. The individual building blocks and their corresponding combinations were probed with regard to their photophysical properties, and the most promising combinations were implemented in dye-sensitized solar cells (DSSCs). Relative to the first porphyrin layer adding the second porphyrin/BODIPY layers increased the overall DSSC efficiency by up to 43 %.