Facile Synthesis and Photophysical Properties of Sphere–Square Shape Amphiphiles Based on Porphyrin–[60]Fullerene Conjugates

Abstract

Molecules constructed from a combination of zero-dimensional ([60]fullerene (C60)) and two-dimensional (porphyrin (Por)) nanobuilding blocks represent an intriguing category of sphere-square "shape amphiphiles". These sphere-square shape amphiphiles possess interesting optoelectronic properties. To efficiently synthesize a large variety of C60-Por shape amphiphiles, a facile route based on Steglich esterification was developed. The synthetic strategy enables the preparation of hydroxy-functionalized Por precursors (9-12) with high purity in a one-pot procedure. All of the C60-Por shape amphiphiles (1-5) can be readily synthesized in good yields through subsequent Steglich esterification with a highly soluble carboxylic acid derivative of methanofullerene (13). Photophysical studies indicated weak electronic coupling between the C60 and Por moieties and suggest an edge-to-face alignment for the moieties. The fluorescence of electronically excited Por portions of each amphiphile was efficiently quenched, which was indicative of electron transfer from (1)Por to the C60 group(s). Increasing the number of C60 groups on the shape amphiphiles led to more pronounced quenching of the Por fluorescence, which indicated the potential for more effective generation of charge-separated species, C60(-.)Por(+.), from the photoexcited C60-Por shape amphiphiles.

Kavli Prize in Nanoscience: T. W. Ebbesen, S. W. Hell, J. B. Pendry / SPSJ International Awards: S. I. Stupp and C.‐S. Hsu

“…The Society of Polymer Science, Japan (SPSJ) presents the SPSJ International Award, which is the society’s highest honor, to scientists over the age of 55 for their contributions to the field and international activities related to the SPSJ. The winners of the 2013 awards are Gert Strobl (University of Freiburg), Shaw Ling Hsu (University of Massachusetts), Samuel I. Stupp (Northwestern University), who was featured here when he won the Ronald Breslow Award for Achievement in Biomimetic Chemistry,4 and Chain‐Shu Hsu (National Chiao Tung University; NCTU), who has reported in Chemistry—An Asian Journal on porphyrin–[60]fullerene conjugates 5. Hsu studied at the National Taiwan Normal University and National Tsing Hua University, and carried out his PhD (awarded in 1987) with Virgil Perec at Case Western Reserve University.…”

Kavli‐Preis in den Nanowissenschaften: T. W. Ebbesen, S. W. Hell, J. B. Pendry / Internationale Preise der SPSJ: S. I. Stupp und C.‐S. Hsu

“…Die japanische Gesellschaft für die Polymerwissenschaften (SPSJ) zeichnet mit ihrem höchsten Preis, dem SPSJ International Award, Wissenschaftler, die älter als 55 Jahre sind, für ihre Beiträge zu diesem Forschungsgebiet und internationale Aktivitäten, die einen Bezug zur SPSJ haben, aus. 2013 gehen die Preise an Gert Strobl (Universität Freiburg), Shaw Ling Hsu (University of Massachusetts), Samuel I. Stupp (Northwestern University) – er wurde in dieser Rubrik vorgestellt, als er den Ronald Breslow Award for Achievement in Biomimetic Chemistry erhalten hatte –4 und Chain‐Shu Hsu (National Chiao Tung University; NCTU), der in Chemistry—An Asian Journal über Porphyrin‐[60]Fulleren‐Konjugate geschrieben hat 5. Hsu studierte an der National Taiwan Normal University und der National Tsing Hua University und promovierte 1987 bei Virgil Perec an der Case Western Reserve University.…”

An unusual self-assembling columnar mesogen prepared by tethering a planar naphthalenediimide acceptor to bent phenothiazine donors

“…Herein, we demonstrate an alternate strategy to control the nanostructure based on tethering mismatched molecular shapes. [44][45][46][47][48][49] Bent-core, or banana-shaped, mesogens, represented by a generic structure shown in Fig. 2a, were first characterised in 1996 by Niori and co-workers 50 and have been explored extensively.…”