Extraordinarily high dark electrical conductivities within processable (porphinato)metal based materials

ORGN 50

Paul R. Frail, pfrail@sas.upenn.edu1, Kimihiro Susumu1, Jennie Fong1, Paul J. Angiolillo, pangioli@sju.edu2, J. M. Kikkawa, kikkawa@physics.upenn.edu3, and Michael J. Therien, therien@sas.upenn.edu1. (1) Department of Chemistry, University of Pennsylvania, 231 South 34th St., Philadelphia, PA 19104-6323, (2) Department of Physics, Saint Joseph's University, 5600 City Avenue, Philadelphia, PA 19131-1395, (3) Department of Physics & Astronomy, University of Pennsylvania, 209 S. 33rd Street, DRL, Philadelphia, PA 19104
Recently, we demonstrated that the radical cation states of highly soluble oligomeric ethyne-bridged (porphinato)zinc(II) structures manifest polaron delocalization lengths approximately 4 times longer than that thus far observed in the classic semi-conducting polymers based on conjugated thiophenes, arylenes, arylethynylenes, pyrroles, and anilines; impressively, EPR spectroscopy shows unequivocally that large magnitude hole polaron mobilities are maintained in these species even at cryogenic temperatures. Reported here is a new class of ethynye-bridged (porphinato)metal oligomers and polymers featuring alkyl-ethylene glyco sidechains. Appropriate modification of macrocycle ancillary substituents gives rise to oligomers and polymers that feature substantial inter-chain electronic coupling. Through the enhancement of the inter-porphyrin electronic copuling amorphous, undoped, solid-state dark conductivities of these materials show a linear increase with increasing oligomer length, >10-4 S cm-1, such that they rival that of porous silicon. The central metal dependency on the inter-chain electronic coupling was also investigated and show competitive solid-state electrical conductivities. Corresponding variable temperature charge transport, mobility, and photoconductivity measurements will also be discussed.
 

Materials, Devices, and Switches
8:00 AM-12:00 PM, Sunday, 10 September 2006 Moscone Center -- Room 132, Oral

Division of Organic Chemistry

The 232nd ACS National Meeting, San Francisco, CA, September 10-14, 2006