1. Optoelectronic Supramolecular Block-Copolymer Assemblies Aided by Donor- Acceptor Interactions Alexander Sidorenko, University of the Sciences in Philadelphia, DMR 0947897 The goal of this EAGER project is the design, synthesis and functional characterization of a new class of nanostructured materials – donor- acceptor supramolecular assemblies (SMA). The third year was dedicated to polymerization of the additive within the matrix of SMA. The additive has triple role: bulky molecule to switch the block copolymer (Figure A, a) morphology from spheres to cylinders (i.e. to form an SMA), to label the SMA domains, and to be a precursor for an electroconductive polymer. We have designed and synthesized bisEDOT molecule (Figure A, b). Based on donor-acceptor interactions, it selectively interacts with a minor block giving the SMA. The SMA demonstrates a curious feature in the fluorescence spectra: the excitation peak at 380 nm splits in two when the SMA is formed (Figure B). The SMA forms perpendicular cylinders in thin films (AFM image, figure C). We have developed a method of gas phase polymerization using Br 2 vapors. The resulting domains enriched with poly(bisEDOT) reveal semiconducting properties with conductive AFM (Figure D). Other electrical properties of regular arrays of nanodots of poly(bisEDOT) are to be probed (future projects). Phase I Phase II Phase III Future projects Block copolymer Supramolecular assembly with a precursor polymerization Array of electroconductive polymer nanodots The goal of this EAGER project is the design, synthesis and functional characterization of a new class of nanostructured materials – donor-acceptor supramolecular assemblies (SMA). A B C D neat poly(bisEDOT) poly(bisEDOT) in SMA

2. Two major activities with notable broader impacts from my grant were: -Four students from South Philadelphia High School and University City High School of Philadelphia have performed a set of experiments under supervision of their teacher Marlene Kim and the PI, Alexander Sidorenko. The topic was directly related to the topic of my grant, namely “ Investigations of 2- (4’-hydroxyphenyl-azo)benzoic acid in various solvents” The students have prepared a poster and presented it at the USciences Research Day (April 7 th, 2012) and also at the ACS Middle Atlantic Regional Meeting (May 31- June 2, 2012). Taking into account that sciences are strongly underrepresented in these traditionally African American schools, participation of the high school students in the “big science” significantly impacted both schools. -The PI has organized a symposium “ Responsive Nanostructured Materials via Self-Assembly ” (PMSE) at the the Spring ACS National Meeting, March, 25-29, 2012 in San-Diego, CA. The symposium hosted 48 speakers (23 invited) during 6 sections (3 full days). -Other broader impact activities: two students involved in research with the PI are graduating with an M.S. degree this summer. Three more undergraduate students has joined the team. Also, the PI has been promoted to the position of Associate Professor (tenured) at the USciences. material Optoelectronic Supramolecular Block-Copolymer Assemblies Aided by Donor- Acceptor Interactions Alexander Sidorenko, University of the Sciences in Philadelphia, DMR 0947897