30 research outputs found
Light-harvesting and electronic contacting capabilities of Ru(II) Ipa rod and star complexes-first principles predictions
Homoleptic ([Ru(L)(3)](2+)) and heteroleptic (Ru(NCS)(2)(bpy)(L)) complexes carrying rigid anchor-cum-spacer ligands (L), comprised of ethynylene-phenylene spacer groups and a designated anchor group, including the isophthalic group (Ipa), have been studied computationally using density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations. The results of the calculations are related to recently measured photophysical properties of selected complexes, and provide theoretical insight into the capabilities of the complexes to mediate interfacial electronic interactions. Opportunities to use the rigid spacer motifs to differentiate structural control and interfacial electronic interactions in heterogeneous systems are discussed, including predictions of promising strategies to enhance long-range interfacial electronic contacting capabilities using star complexes with new anchor group motifs
Large Footprint Pyrene Chromophores Anchored to Planar and Colloidal Metal Oxide Thin Films
Sensitization and binding of a large footprint pyrene chromophore to planar (sapphire) and colloidal metal oxide films (TiO2 and ZrO2) is investigated. The model compound combines a 1-pyrenyl-ethynylenephenylene unit with a new adamantane-tripodal linker that binds to the surface. The linker design, combining a large footprint (2 nm2) of the tripodal linker with the meta position of the COOH anchoring groups, was suggested from atomistic models, and it aims to provide improved spacing control. The pyrene chromophore unit provides a probe of sensitizer−sensitizer interactions through its propensity to form excimers, unless neighboring pyrene units are sufficiently spaced (≥3.5 Å). Absorption and fluorescence studies, and a comparison with a pyrene−rigid rod model compound, suggest that the new tripodal anchor group allows spacing control on planar surfaces. On colloidal films, the linker provides spacing control at low surface coverage but sensitizer−sensitizer interactions are still observed on colloidal films at high surface coverage. Implications for the functionalization of metal oxide films in hybrid molecule−metal oxide semiconductor material systems are discussed
Fluorescence Enhancement of Di-<i>p</i>-tolyl Viologen by Complexation in Cucurbit[7]uril
A viologen derivative, 1,1′-di-<i>p</i>-tolyl-(4,4′-bipyridine)-1,1′-diium
dichloride (DTV<sup>2+</sup>), was studied in solution and encapsulated
in cucurbit[7]Âuril (CB7), a macrocyclic host. Upon encapsulation,
DTV<sup>2+</sup> exhibited dramatically enhanced fluorescence. Aqueous
solutions of DTV<sup>2+</sup> were weakly fluorescent (Φ = 0.01,
Ï„ < 20 ps), whereas the emission of the DTV<sup>2+</sup>@2CB7
complex was enhanced by 1 order of magnitude (Φ = 0.12, τ
= 0.7 ns) and blue-shifted by 35 nm. Similar properties were observed
in the presence of NaCl. DTV<sup>2+</sup> in a polyÂ(methyl methacrylate)
matrix was fluorescent with a spectrum similar to that observed for
the complex in solution. <sup>1</sup>H NMR and UV–vis titrations
indicated that the DTV<sup>2+</sup>@2CB7 complex is formed in aqueous
solutions with complexation constants <i>K</i><sub>1</sub> = (1.2 ± 0.3) × 10<sup>4</sup> M<sup>–1</sup> and <i>K</i><sub>2</sub>= (1.0 ± 0.4) × 10<sup>4</sup> M<sup>–1</sup> in water. Density functional theory and configuration
interaction singles calculations suggested that the hindrance of the
rotational relaxation of the S<sub>1</sub> state of DTV<sup>2+</sup> caused by encapsulation within the host or a polymer matrix plays
a key role in the observed emission enhancement. The absorption and
emission spectra of DTV<sup>2+</sup>@2CB7 in water exhibited a large
Stokes shift (ΔSt ∼ 9000 cm<sup>–1</sup>) and
no fine structure. DTV<sup>2+</sup> is a good electron acceptor [<i>E</i>°(DTV<sup>2+</sup>/DTV<sup>•+</sup>) = −0.30
V vs Ag/AgCl] and a strong photooxidant [<i>E</i>°(DTV*<sup>2+</sup>/DTV<sup>•+</sup>) = 0.09 V vs NHE])
Vibrational Spectroscopy on Photoexcited Dye-Sensitized Films via Pump-Degenerate Four-Wave Mixing
Molecular
sensitization of semiconductor films is an important
technology for energy and environmental applications including solar
energy conversion, photocatalytic hydrogen production, and water purification.
Dye-sensitized films are also scientifically complex and interesting
systems with a long history of research. In most applications, photoinduced
heterogeneous electron transfer (HET) at the molecule/semiconductor
interface is of critical importance, and while great progress has
been made in understanding HET, many open questions remain. Of particular
interest is the role of combined electronic and vibrational effects
and coherence of the dye during HET. The ultrafast nature of the process,
the rapid intramolecular vibrational energy redistribution, and vibrational
cooling present complications in the study of vibronic coupling in
HET. We present the application of a time domain vibrational spectroscopyî—¸pump-degenerate
four-wave mixing (pump-DFWM)î—¸to dye-sensitized solid-state
semiconductor films. Pump-DFWM can measure Raman-active vibrational
modes that are triggered by excitation of the sample with an actinic
pump pulse. Modifications to the instrument for solid-state samples
and its application to an anatase TiO<sub>2</sub> film sensitized
by a Zn-porphyrin dye are discussed. We show an effective combination
of experimental techniques to overcome typical challenges in measuring
solid-state samples with laser spectroscopy and observe molecular
vibrations following HET in a picosecond time window. The cation spectrum
of the dye shows modes that can be assigned to the linker group and
a mode that is localized on the Zn-phorphyrin chromophore and that
is connected to photoexcitation