Dataset Information

Push-Pull N,N-Diphenylhydrazones Bearing Bithiophene or Thienothiophene Spacers as Nonlinear Optical Second Harmonic Generators and as Photosensitizers for Nanocrystalline TiO2 Dye-Sensitized Solar Cells.

ABSTRACT: A series of push-pull heterocyclic N,N-diphenylhydrazones were prepared to study the effect of structural modifications (different ?-spacers and electron-withdrawing groups) on the optical (linear and nonlinear) and electronic properties of the molecules. The photovoltaic response of dye-sensitized solar cells assembled using nanocrystalline titania photosensitized with the synthesized dyes was also studied. These heterocyclic push-pull conjugated dyes involve N,N-diphenylhydrazones as electron donors linked to bithiophene or thieno[3,2-b]thiophene spacers and were functionalized with carboxylic acid, cyanoacetic acid, or dicyanovinyl acceptor groups. A combination of Suzuki-Miyaura cross-coupling, Vilsmeier formylation, and condensation reactions was used to synthesize the intermediates and final products. Density functional theory (DFT) and time dependent-DFT calculations were used to obtain information on conformation, electronic structure, and electron distribution, both for the free dyes and those adsorbed on TiO2. The results of this multidisciplinary study indicate that dyes 5b and 6b have the strongest second-order nonlinear optical response with hyperpolarizability values in the range of ? = 2330 × 10-30 to 2750 × 10-30 esu, whereas photovoltaic power conversion efficiencies reach values in the range of 0.7-3.0% for dyes 5a-b and 7c and were enhanced by coadsorbing deoxycholic acid (0.8-5.1%).

SUBMITTER: M Fernandes SS

PROVIDER: S-EPMC6210073 | biostudies-literature | 2018 Oct

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

Push-Pull N,N-Diphenylhydrazones Bearing Bithiophene or Thienothiophene Spacers as Nonlinear Optical Second Harmonic Generators and as Photosensitizers for Nanocrystalline TiO2 Dye-Sensitized Solar Cells.

M Fernandes Sara S SS Belsley Michael M Pereira Ana I AI Ivanou Dzmitry D Mendes Adélio A Justino Licínia L G LLG Burrows Hugh D HD Raposo M Manuela M MMM

ACS omega 20181009 10

A series of push-pull heterocyclic N,N-diphenylhydrazones were prepared to study the effect of structural modifications (different π-spacers and electron-withdrawing groups) on the optical (linear and nonlinear) and electronic properties of the molecules. The photovoltaic response of dye-sensitized solar cells assembled using nanocrystalline titania photosensitized with the synthesized dyes was also studied. These heterocyclic push-pull conjugated dyes involve N,N-dip ...[more]

PMID: 30411023

Similar Datasets

Project description:A new generation of octahedral iron(ii)-N-heterocyclic carbene (NHC) complexes, employing different tridentate C^N^C ligands, has been designed and synthesized as earth-abundant photosensitizers for dye sensitized solar cells (DSSCs) and related solar energy conversion applications. This work introduces a linearly aligned push-pull design principle that reaches from the ligand having nitrogen-based electron donors, over the Fe(ii) centre, to the ligand having an electron withdrawing carboxylic acid anchor group. A combination of spectroscopy, electrochemistry, and quantum chemical calculations demonstrate the improved molecular excited state properties in terms of a broader absorption spectrum compared to the reference complex, as well as directional charge-transfer displacement of the lowest excited state towards the semiconductor substrate in accordance with the push-pull design. Prototype DSSCs based on one of the new Fe NHC photosensitizers demonstrate a power conversion efficiency exceeding 1% already for a basic DSSC set-up using only the I-/I3 - redox mediator and standard operating conditions, outcompeting the corresponding DSSC based on the homoleptic reference complex. Transient photovoltage measurements confirmed that adding the co-sensitizer chenodeoxycholic acid helped in improving the efficiency by increasing the electron lifetime in TiO2. Time-resolved spectroscopy revealed spectral signatures for successful ultrafast (<100 fs) interfacial electron injection from the heteroleptic dyes to TiO2. However, an ultrafast recombination process results in undesirable fast charge recombination from TiO2 back to the oxidized dye, leaving only 5-10% of the initially excited dyes available to contribute to a current in the DSSC. On slower timescales, time-resolved spectroscopy also found that the recombination dynamics (longer than 40 μs) were significantly slower than the regeneration of the oxidized dye by the redox mediator (6-8 μs). Therefore it is the ultrafast recombination down to fs-timescales, between the oxidized dye and the injected electron, that remains as one of the main bottlenecks to be targeted for achieving further improved solar energy conversion efficiencies in future work.

Dataset Information

Push-Pull N,N-Diphenylhydrazones Bearing Bithiophene or Thienothiophene Spacers as Nonlinear Optical Second Harmonic Generators and as Photosensitizers for Nanocrystalline TiO2 Dye-Sensitized Solar Cells.

Publications

Push-Pull <i>N</i>,<i>N</i>-Diphenylhydrazones Bearing Bithiophene or Thienothiophene Spacers as Nonlinear Optical Second Harmonic Generators and as Photosensitizers for Nanocrystalline TiO<sub>2</sub> Dye-Sensitized Solar Cells.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets