The nature of charge carriers in conjugated polymers was elucidated through optical spectroscopy following single- and multielectron reduction of 2,7-(9,9-dihexylfluorene) oligomers, F(n), n = 1-10, yielding spectra with the two bands typical of polarons upon single reduction. For short oligomers addition of a second electron gave a single band demonstrating the classic polaron-bipolaron transition. However, for long oligomers double reductions yielded spectra with two bands, better described as two polarons, possibly residing side-by-side in the F(n) chains. The singly reduced anions do not appear to delocalize over the entire length of the longer conjugated systems; instead they are polarons occupying approximately four fluorene repeat units. The polarons of F(3) and F(4) display sharp absorption bands, but for longer oligomers the bands broaden, possibly due to fluctuations of the lengths of these unconfined polarons. DFT calculations with long-range-corrected functionals were fully consistent with the experiments describing polarons in anions, bipolarons in dianions of short oligomers, and side-by-side polarons in dianions of long oligomers, while results from standard functionals were not compatible with the experimental results. The computations found F(10)(2-), for example, to be an open-shell singlet ( ≈ 1), with electrons in two side-by-side orbitals, while dianions of shorter oligomers experienced a gradual transition to bipolarons with states of intermediate character at intermediate lengths. The energies and extinction coefficients of each anionic species were measured by ultraviolet-visible-near-infrared absorption spectroscopy with chemical reduction and pulse radiolysis. Reduction potentials determined from equilibria mirrored oxidation potentials reported by Chi and Wegner. Anions of oligomers four or more units in length contained vestigial neutral (VN) absorption bands that arise from neutral parts of the chain. Energies of the VN bands correspond to those of oligomers shorter by four units.

Photoexcitation of conjugated poly-2,7-(9,9-dihexylfluorene) polyfluorenes with naphthylimide (NI) and anthraquinone (AQ) electron-acceptor end traps produces excitons that form charge transfer states at the end traps. Intramolecular singlet exciton transport to end traps was examined by steady state fluorescence for polyfluorenes of 17-127 repeat units in chloroform, dimethylformamide (DMF), tetrahydrofuran (THF), and p-xylene. End traps capture excitons and form charge transfer (CT) states at all polymer lengths and in all solvents. The CT nature of the end-trapped states is confirmed by their fluorescence spectra, solvent and trap group dependence, and DFT descriptions. Quantum yields of CT fluorescence are as large as 46%. This strong CT emission is understood in terms of intensity borrowing. Energies of the CT states from onsets of the fluorescence spectra give the depths of the traps which vary with solvent polarity. For NI end traps, the trap depths are 0.06 (p-xylene), 0.13 (THF), and 0.19 eV (CHCl3). For AQ, CT fluorescence could be observed only in p-xylene where the trap depth is 0.27 eV. Quantum yields, emission energies, charge transfer energies, solvent reorganization, and vibrational energies were calculated. Fluorescence measurements on chains >100 repeat units indicate that end traps capture ∼50% of the excitons, and that the exciton diffusion length is LD = 34 nm, which is much larger than diffusion lengths reported in polymer films or than previously known for diffusion along isolated chains. The efficiency of exciton capture depends on chain length but not on trap depth, solvent polarity, or which trap group is present.

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The chemical and biological impacts of anthropogenic physical modifications (i.e., channelization, dredging, bulkhead, and jetty construction) to tributaries were assessed on New York's Long Island South Shore Estuary. Water-quality data collected on Carmans, Patchogue, and Swan Rivers from 1997 to 2005 indicate no significant differences in nutrient levels, temperature, or pH among the rivers, but significant differences in light transmittance, dissolved oxygen (DO), salinity, and sediments were observed. Patchogue River (PR) and Swan River (SR) were significantly more saline than Carmans River (CR), PR and SR had less light transmittance than CR, and both exhibited severe warm season hypoxia. CR was rarely hypoxic and only at the lower layer of the deepest station in warm seasons. Deep stations on PR had hypoxic readings year round, but the shallower SR was well-oxygenated at all stations after the fall turnover. There were wide diel and seasonal variations in chlorophyll a on each river, and measurements were significantly higher at poorly flushed stations. In warm seasons, this often resulted in hyperventilation with supersaturated DO in the upper water column on sunny days, and suboxic conditions at nights and/or in deeper layers. PR sediments were anoxic, SR sediments ranged from normal to anoxic, and CR sediments were normal at all stations. Polyaromatic hydrocarbon concentrations in PR sediments were over three orders of magnitude higher than SR and CR sediments. Benthic invertebrate assessment of species richness, biotic index, and Ephemeroptera, Plecoptera and Trichoptera richness indicated that PR was severely impacted, SR ranged from slightly to severely impacted, and CR ranged from nonimpacted to slightly impacted. Diversity and abundance of plankton were comparable on SR and CR, and were significantly higher than on PR. The data indicate that nutrients do not play a major role in hypoxia in these estuarine tributaries but that physical forces dominate. The narrow inlets, channelization, and abrupt changes in depth near the inlets of PR and SR foster hypoxic conditions by inducing salinity stratification that limits vertical mixing and by restricting horizontal water mass exchange with the bay. The study suggests that other tributaries with such physical modifications should be examined to assess the temporal and spatial extent of hypoxia.