The effect of ethynyl substitution and cyclopenta fusion on the ultraviolet absorption spectra of polycyclic aromatic hydrocarbons.
We have examined the UV spectra of six newly-synthesized ethynyl-PAH (1-ethynylnaphthalene, 5-ethynylacenaphthylene, 1-ethynylanthracene, 9-ethynylphenanthrene, 3-ethynylfluoranthene, and 1-ethynylpyrene) and five corresponding CP-PAH (acenaphthylene, aceanthrylene, acephenanthrylene, cyclopenta[cd]fluoranthene, and cyclopenta[cd]pyrene) and have found the following systematic behavior: ethynyl-substitution results in average bathochromic shifts of 5 nm for the lower-wavelength beta- and beta'-bands and of 18 nm for the higher-wavelength p-band, as well as an amplification of the p-band with respect to the beta-band; the addition of a peripheral cyclopenta ring results in average bathochromic shifts of 7 nm in the beta-band, 16 nm in the beta'-band, and 44 nm in the p-band, compared to the wavelengths in the corresponding unsubstituted PAH. The addition of a cyclopenta ring also decreases the resolution of vibrational fine structure in the cases where the fine structure is particularly intense in the spectrum of the unsubstituted PAH. The effects of ethynyl substitution on the UV spectra of PAH are sufficiently consistent that new ethynyl-PAH should be identifiable based on their UV spectra alone.
Marsh
N D
ND
Department of Mechanical and Aerospace Engineering, Princeton University, NJ 08544, USA.
Mikolajczak
C J
CJ
Wornat
M J
MJ
D000073:Acenaphthenes / Q000737:chemistry; D000873:Anthracenes / Q000737:chemistry*; D005449:Fluorenes / Q000737:chemistry; D015394:Molecular Structure; D009281:Naphthalenes / Q000737:chemistry*; D010616:Phenanthrenes / Q000737:chemistry; D011084:Polycyclic Aromatic Hydrocarbons / Q000737:chemistry*; D011721:Pyrenes / Q000737:chemistry; D013056:Spectrophotometry, Ultraviolet / Q000379:methods
C096666:9-ethynylphenanthrene; D000073:Acenaphthenes; D000873:Anthracenes; D005449:Fluorenes; D009281:Naphthalenes; D010616:Phenanthrenes; D011084:Polycyclic Aromatic Hydrocarbons; D011721:Pyrenes; C042553:acenaphthylene; C044587:aceanthrylene; C065012:2-ethynylnaphthalene; C016328:cyclopenta(c,d)pyrene; C042881:1-ethynylpyrene; C119992:acephenanthrylene