NDLI: Binary ionic porphyrin nanosheets: electronic and light-harvesting properties regulated by crystal structure

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Nanoscale Vol - 4 Issue - 4

Nanoscale Vol - 4 Issue - 3

Nanoscale Vol -3

Nanoscale Vol -2

Nanoscale Vol -1

Binary ionic porphyrin nanosheets: electronic and light-harvesting properties regulated by crystal structure

Content Provider	Royal Society of Chemistry (RSC)
Author	Swartzentruber, Brian S. Shelnutt, John A. Mercado, Brandon Q. Jacobsen, John L. Martin, Kathleen E. Swol, Frank Busani, Tito Tian, Yongming Beavers, Christine M. Medforth, Craig J.
Copyright Year	2012
Abstract	Crystalline solids self-assembled from anionic and cationic porphyrins provide a new class of multifunctional optoelectronic micro- and nanomaterials. A 1 : 1 combination of zinc(II) tetra(4-sulfonatophenyl)porphyrin (ZnTPPS) and tin(IV) tetra(N-methyl-4-pyridiniumyl)porphyrin (SnTNMePyP) gives porphyrin nanosheets with high aspect ratios and varying thickness. The room temperature preparation of the nanosheets has provided the first X-ray crystal structure of a cooperative binary ionic (CBI) solid. The unit cell contains one and one-half molecules of aquo-ZnTPPS4− (an electron donor) and three half molecules of dihydroxy-SnTNMePyP4+ (an electron acceptor). Charge balance in the solid is reached without any non-porphyrinic ions, as previously determined for other CBI nanomaterials by non-crystallographic means. The crystal structure reveals a complicated molecular arrangement with slipped π–π stacking only occurring in isolated dimers of one of the symmetrically unique zinc porphyrins. Consistent with the crystal structure, UV-visible J-aggregate bands indicative of exciton delocalization and extended π–π stacking are not observed. XRD measurements show that the structure of the Zn/Sn nanosheets is distinct from that of Zn/Sn four-leaf clover-like CBI solids reported previously. In contrast with the Zn/Sn clovers that do exhibit J-aggregate bands and are photoconductive, the nanosheets are not photoconductive. Even so, the nanosheets act as light-harvesting structures in an artificial photosynthesis system capable of reducing water to hydrogen but not as efficiently as the Zn/Sn clovers.
Starting Page	1695
Ending Page	1700
Page Count	6
File Format	HTM / HTML PDF
ISSN	20403364
Volume Number	4
Issue Number	5
Journal	Nanoscale
DOI	10.1039/c2nr11826b
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Optoelectronics Exciton Central Bureau of Investigation Redox Nanomaterials J-aggregate CBI Zinc The Room (film) X-ray crystallography Porphyrin Artificial photosynthesis Tin The Unit Electron acceptor Hydrogen bond
Content Type	Text
Resource Type	Article
Subject	Nanoscience and Nanotechnology

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