Push–Pull Porphyrin-Containing Polymers: Materials
Exhibiting Ultrafast Near-IR Photophysics
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Abstract
Four push–pull polymers of
structure (CC–<b>[Zn]</b>–CC–<b>A</b>)<sub><i>n</i></sub> (<b>A</b> = isoindigo
(<b>P1</b>), bis(α-methylamino-1,4-benzene)quinone
(<b>P2</b>), 2-(<i>N</i>-methylamino-1,4-benzene)-<i>N</i>-1,4-benzene-maleimide (<b>P3</b>), and 2,2′-anthraquinone (<b>P4</b>); <b>[Zn]</b> = [bis(<i>meso</i>-aryl)porphyrin]zinc(II) = donor) and
models <b>M1</b> and <b>M2</b> (<b>A</b>′–CC–<b>[Zn]</b>–CC–<b>A</b>′; <b>A</b>′ = respectively naphtoquinone and 2-anthraquinone)
were prepared and characterized (<sup>1</sup>H and <sup>13</sup>C
NMR, elemental analysis, GPC, TGA, cyclic voltammetry, steady state
and ultrafast time-resolved UV–vis and emission spectroscopy)
and studied by density functional theory (DFT) and time-dependent
DFT (TDDFT) in order to address the nature of the low-lying singlet
and triplet excited states. <b>P1</b> (fully conjugated polymer), <b>P2</b> (formally nonconjugated but exhibit strong electronic communication
accross the chain) and <b>P4</b> (formally nonconjugated but
local conjugation between the donor and acceptor) are near-IR emitters
(λ<sub>max</sub> > 750 nm). <b>M1</b> and <b>M2</b> are mono-CC–<b>[Zn]</b>–CC species,
and <b>P3</b> exhibits a very modest CT contribution (as maleimide
is a weak acceptor) and are not near-IR emitters. The nature of the
S<sub>1</sub> and T<sub>1</sub> excited states are CT processes donor*
→ acceptor. In <b>P1</b>–<b>P4</b>, a dual
fluorescence (7.7 < τ<sub>F</sub> < 770 ps; except one
value at 2.5 ns; <b>P3</b>) is depicted, which are assigned
to fluorescences arising from the terminal and central units of the
polymers identified from the comparison with <b>M1</b> and <b>M2</b>. The high and low energy fluorescences are respectively
short (77 < τ<sub>F</sub> < 166 ps) and long-lived (688
< τ<sub>F</sub> < 765 ps) suggesting S<sub>1</sub> energy
transfers with rates, k<sub>ET</sub>, of 7.1 (<b>P1</b>), 12
(<b>P2</b>) and 4.5 (ns)<sup>−1</sup> (<b>P4</b>). The fs transient absorption spectra exhibit particularly very
short triplet lifetimes (2.3 < τ<sub>T1</sub> < 87 ns)
explaining the absence of phosphorescence. Also ultrafast lifetimes
(85 < τ < 1290 fs) for species excited in the 0–0
peak of the Q-band (650 nm; i.e., ππ* porphyrin level)
indicating its rather efficient nonradiative deactivation (S<sub><i>n</i></sub> ∼ > S<sub>1</sub> and S<sub><i>n</i></sub> ∼ > <i>T</i><sub>m</sub>). When cooling
takes
place or the solution concentration is increased, new red-shifted
fluorescence bands appear, evidencing aggregate formation. Both fluorescence
and transient absorption lifetimes of <b>P1</b>–<b>P4</b> become shorter and their band intensity lower. Finally,
the position of the optically silent phosphorescence has been predicted
to be in the 1300 (<b>P1</b>, <b>P2</b>) and 1000 nm (<b>P3</b>, <b>P4</b>) zones (DFT)