Thin films of polymerized rodlike phthalocyanine aggregates

Carrie L. Donley, Wei Xia, Britt A. Minch, Rebecca A P Zangmeister, Anthony S. Drager, Kenneth Nebesny, David F. O'Brien, Neal R Armstrong

Research output: Contribution to journalArticle

28 Citations (Scopus)

Abstract

We report here the synthesis, characterization, and thin film formation of a polymerizable octa-substituted phthalocyanine (Pc) with styryl-terminated side chains, CuPc(OCH2CH2OCH2CH=CHPh) 8, 2,3,9,10,16,17,23,24-octakis(2-cinnamyloxyethoxy) phthalocyaninato copper(II) (1). We compare this Pc with a previously discussed phthalocyanine, also possessing styryl groups at the termini of the side chains, but with one alkoxy group in the side chain removed, CuPc(OCH 2CH2CH=CHPh)8 (2) (J. Am. Chem. Soc. 2001, 123, 3595). Both 1 and 2 are related to the octa-substituted phthalocyanine CuPc(OCH2CH2OBz)8, 2,3,9,10,16,17,23, 24-octakis (2-benzyloxyethoxy) phthalocyaninato copper(II) (3), which has been shown to form highly coherent rodlike aggregates in Langmuir-Blodgett (LB) films, with excellent control of rod orientation (J. Am. Chem. Soc. 1999, 121, 8628; Langmuir 2001, 17, 7071). Irradiation of the styryl π-π* absorbance bands (254 nm) for horizontally transferred LB films of 1 and 2 results in stabilization of their rodlike aggregates, through formation of cyclobutane links between adjacent side chains. Compound 1 shows a maximum 75% conversion of styryl groups versus ca. 55% conversion in 2. Polymerized thin films of 1 are insoluble in common solvents, and "ribbonlike" features can be lithographically produced with widths of 8 microns and heights of ca. 20 nm, maintaining control over the orientation of the Pc rods in the patterned features. Long-range order in both the as-deposited, annealed, and polymerized thin films was confirmed by atomic force microscopy and X-ray reflectometry, and small differences in the orientation of individual Pc's, between films of 1 and 3, were determined by transmission and reflectance Fourier transform infrared spectroscopy. Higher dark and photoconductivities and higher electrical anisotropies were observed in films of 1, after annealing and polymerization, versus those seen for films of 3.

Original languageEnglish (US)
Pages (from-to)6512-6522
Number of pages11
JournalLangmuir
Volume19
Issue number16
DOIs
StatePublished - Aug 5 2003

Fingerprint

Langmuir Blodgett films
Thin films
thin films
Copper
Langmuir-Blodgett films
Photoconductivity
rods
Fourier transform infrared spectroscopy
Cyclobutanes
Atomic force microscopy
Anisotropy
cyclobutane
Stabilization
copper
Polymerization
Irradiation
Annealing
X rays
photoconductivity
polymerization

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Colloid and Surface Chemistry

Cite this

Donley, C. L., Xia, W., Minch, B. A., Zangmeister, R. A. P., Drager, A. S., Nebesny, K., ... Armstrong, N. R. (2003). Thin films of polymerized rodlike phthalocyanine aggregates. Langmuir, 19(16), 6512-6522. https://doi.org/10.1021/la034271+

Thin films of polymerized rodlike phthalocyanine aggregates. / Donley, Carrie L.; Xia, Wei; Minch, Britt A.; Zangmeister, Rebecca A P; Drager, Anthony S.; Nebesny, Kenneth; O'Brien, David F.; Armstrong, Neal R.

In: Langmuir, Vol. 19, No. 16, 05.08.2003, p. 6512-6522.

Research output: Contribution to journalArticle

Donley, CL, Xia, W, Minch, BA, Zangmeister, RAP, Drager, AS, Nebesny, K, O'Brien, DF & Armstrong, NR 2003, 'Thin films of polymerized rodlike phthalocyanine aggregates', Langmuir, vol. 19, no. 16, pp. 6512-6522. https://doi.org/10.1021/la034271+
Donley CL, Xia W, Minch BA, Zangmeister RAP, Drager AS, Nebesny K et al. Thin films of polymerized rodlike phthalocyanine aggregates. Langmuir. 2003 Aug 5;19(16):6512-6522. https://doi.org/10.1021/la034271+
Donley, Carrie L. ; Xia, Wei ; Minch, Britt A. ; Zangmeister, Rebecca A P ; Drager, Anthony S. ; Nebesny, Kenneth ; O'Brien, David F. ; Armstrong, Neal R. / Thin films of polymerized rodlike phthalocyanine aggregates. In: Langmuir. 2003 ; Vol. 19, No. 16. pp. 6512-6522.
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