Template-Directed Synthesis of a Conjugated Zinc Porphyrin Nanoball

Abstract

We report the template-directed synthesis of a π-conjugated 14-porphyrin nanoball. This structure consists of two intersecting nanorings containing six and 10 porphyrin units. Fluorescence upconversion spectroscopy experiments demonstrate that electronic excitation delocalizes over the whole three-dimensional π system in less than 0.3 ps if the nanoball is bound to its templates or over 2 ps if the nanoball is empty.

Multiple‐Porphyrin Functionalized Hexabenzocoronenes

“…Hexaphenylbenzenes (HPBs) and their oxidized derivatives hexa‐ peri ‐hexabenzocoronenes (HBCs) have received tremendous attention during the past 20 years in materials chemistry, for example in molecular electronics and nonlinear optics . They have proven to be a suitable scaffold for catalytic applications, the design of supramolecular architectures, as well as a perfectly sized template for the preparation of nano‐ring and nano‐ball structures. In contrast, porphyrins and related macrocycles, which are found in nature in different appearances such as heme, chlorophyll, or bacteriochlorophyll, have attracted the attention from the scientific community ever since their discovery.…”

“…Hexaphenylbenzenes (HPBs) and their oxidized derivatives hexa-peri-hexabenzocoronenes (HBCs)h ave received tremendous attention during the past 20 years in materials chemistry, for example in moleculare lectronics and nonlinearo ptics. [1][2][3][4][5] They have provent obeasuitable scaffold for catalytic applications, [6,7] the design of supramolecular architectures, [8,9] as well as ap erfectly sized template fort he preparation of nanoring [10,11] and nano-ball [12] structures.I nc ontrast, porphyrins and related macrocycles,w hich are foundi nn ature in different appearances such as heme, chlorophyll,o rb acteriochlorophyll, have attracted the attention from the scientific community ever since their discovery.D ue to their photophysical charac-teristics, featuring high extinction coefficients in the visiblelight region, porphyrins have provent ob ea ni deal chromophoref or light-harvesting architectures. [13][14][15][16][17][18][19][20][21] Thec ombination of both buildingb locks, porphyrins and HPBs, was initiated in 2002 by the synthesis of aH PB core, surrounded by six directly meso-attached porphyrins.…”

Grafting Copper and Gallium Corroles onto Zinc Oxide Nanoparticles

“…In order to improve the harvesting of solar energy in a broad spectral region, it is important to extend the corrole energy absorption across the visible spectrum as much as possible. As already documented, β ‐pyrrolic modification and extension of the porphyrin π system significantly broadens and redshifts the light absorption . In this context, very recently, the expansion of corrole aromaticity was reported by our group, affording a number of corrole derivatives in good yields ,,…”

“…As already documented, β-pyrrolic modification and extension of the porphyrin π system significantly broadens and redshifts the light absorption. [10][11][12][13] In this context, very recently, the expansion of corrole aromaticity was reported by our group, affording a number of corrole derivatives in good yields. [8,14,15] Immobilization of the absorbing dye molecules onto the surface of semiconducting metal oxide nanoparticles, which collectively act as the working electrode of a dye-sensitized solar cell (DSSC), is crucial for initiating an electrical current via the injection of electrons from the dye into the conduction band of the metal oxide.…”

Synthesis and Properties of Porphyrin Nanotubes

“…[61,64 -66] Beyond the two-dimensionality of the porphyrin nanorings, we prepared a spiro-fused array of 11 porphyrin units, [67] and a porphyrin nanoball consisting of two intersecting nanorings containing six and ten porphyrin units. [68] In both nanostructures, fluorescence upconversion spectroscopy experiments demonstrated rapid exciton delocalization (within 0.3 ps), indicating extensive electronic communication around the entire πsystem.…”