Molecular engineering of carbazole-fluorene sensitizers for high open-circuit voltage DSSCs: Synthesis and performance comparison with iodine and cobalt electrolytes

Massin, Julien; Ducasse, Laurent; Abbas, Mamatimin; Hirsch, Lionel; Toupance, Thierry; Olivier, Céline

doi:10.1016/j.dyepig.2015.02.020

Cited by 25 publications

(6 citation statements)

References 32 publications

(51 reference statements)

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“…Here, two different techniques: (a) the standardization-based technique 45 and (b) the Euclidean distance approach 41 were used. A good number of dyes already exist from the TPA chemical class and successful modeling was already performed for phenothiazine 22 and carbazole 46,47 dyes. Therefore, we have concentrated on designing new dyes for the chemical class of tetrahydroquinoline, indoline and N,N′-dialkylaniline employing their respective QSPR models as those dyes are the least explored ones under DSSCs.…”

Section: Methodsmentioning

confidence: 99%

In silico designing of power conversion efficient organic lead dyes for solar cells using todays innovative approaches to assure renewable energy for future

2017

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Advances in solar cell technology require designing of new organic dye sensitizers for dye-sensitized solar cells with high power conversion efficiency to circumvent the disadvantages of silicon-based solar cells. In silico studies including quantitative structureproperty relationship analysis combined with quantum chemical analysis were employed to understand the primary electron transfer mechanism and photo-physical properties of 273 arylamine organic dyes from 11 diverse chemical families explicit to iodine electrolyte. The direct quantitative structure-property relationship models enable identification of the essential electronic and structural attributes necessary for quantifying the molecular prerequisites of 11 classes of arylamine organic dyes, responsible for high power conversion efficiency of dye-sensitized solar cells. Tetrahydroquinoline, N,N′-dialkylaniline and indoline have been least explored classes under arylamine organic dyes for dye-sensitized solar cells. Therefore, the identified properties from the corresponding quantitative structure-property relationship models of the mentioned classes were employed in designing of "lead dyes". Followed by, a series of electrochemical and photo-physical parameters were computed for designed dyes to check the required variables for electron flow of dye-sensitized solar cells. The combined computational techniques yielded seven promising lead dyes each for all three chemical classes considered. Significant (130, 183, and 46%) increment in predicted %power conversion efficiency was observed comparing with the existing dye with highest experimental %power conversion efficiency value for tetrahydroquinoline, N,N′-dialkylaniline and indoline, respectively maintaining required electrochemical parameters.

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Section: Methodsmentioning

confidence: 99%

In silico designing of power conversion efficient organic lead dyes for solar cells using todays innovative approaches to assure renewable energy for future

2017

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“…To synthesize cobalt(Ⅱ/Ⅲ) bis[6-(1H-pyrazol-1-yl)-2,2'-bipyridine], [Co(bpypz)2] 2+/3+ , the ligand bpypz has been prepared according to the synthetic procedures reported previously. 5 [Co(bpypz)2](B(CN)4)2: 6 Bpypz ligand (200 mg, 0.90 mmol) was dissolved in methanol (3 mL) under N2 atmosphere. After complete dissolution of bpypz ligand, CoCl2 6H2O (96 mg, 0.41 mmol) was added to the solution and refluxed for 2 h. After cooling to room temperature, KB(CN)4 (139 mg, 0.70 mmol) was added to the mixture.…”

Section: S4mentioning

confidence: 99%

“…The slurry was vigorously stirred for 15 min then filtered and washed several times with water then dried.Yield 99%; the spectroscopic data were identical with published before. 2FreeGD2: 2-{3- [5,10,15,porphinato zinc (II)-2-yl]-allylidene}malonic acid 3-[5,10,15,20-tetra(3,5-dimethylphenyl)porphyrin-2'-yl]allylaldehyde (100 mg, 1.3 x 10 -4 mol) and malonic acid (132 mg, 1.3 x 10 -3 mol) were dissolved in THF (3 mL), then acetic acid (3 mL) was added followed by ammonium acetate (100 mg, 1.3 x 10 -3 mol). 3 The resulting mixture was stirred at 70 o C for 3 h then poured into cold water.…”

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confidence: 99%

The Significant Effect of Electronic Coupling on Electron Transfer between Surface-Bound Porphyrins and Co^2+/3+ Complex Electrolytes

Cho¹,

Mozer²,

Wagner³

et al. 2020

Meet. Abstr.

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The coordination of metal ions such as Zn2+ with the π-conjugated porphyrin ring is one of the simplest and the most often used structural modification to alter the electronic nature of a molecule without significantly affecting its size or geometry. The question answered in this work is to what extent electron transfer rates between a surface bound Zn2+porphyrin and a cationic electron donor (Co2+ polypyridyl complexes) is affected by the altered electrostatic interaction between the two molecules at the same electrochemical driving force (DG°). To date, very few studies addressed the effect of electrostatic intermolecular interactions on electron transfers explicitly. We measured electron transfer rates between 4 porphyrin (2 freebase and 2 Zn porphyrin) molecules attached to TiO2 electrodes and 5 Co2+/3+ complexes dissolved in electrolytes covering a DG° range of close to 1 V. The porphyrin molecules were photo-excited at 532 nm leading to an oxidized porphyrin and an electron injected into the conduction band of the TiO2 electrode. The rate of electron transfer was been determined using transient absorption spectroscopy (TAS) by monitoring the absorption change of the oxidized porphyrin molecules in the presence of the redox mediators in various concentrations. The measured rate constants were fitted to Marcus theory. We have found that even the simplest dimethyl substitution on the bipyridine ligands of the Co2+/3+ complexes resulted in a significant decrease in electron coupling. To account for the variation in electron coupling among the Co2+/3+ complexes, the electron rate constants were normalized by the square of the ratio of the electronic coupling factors. The normalized rate constants showed a 30% increase in electron coupling of the free base porphyrins with Co2+/3+ compared to the electronic coupling between Zn porphyrins and Co2+/3+. Increased coupling suggests shorter donor – acceptor distance or better wavefunction overlap, which could be due to electrostatic interaction of the Co2+ with the lone pairs of the free base porphyrin, which interaction is blocked by Zn2+ coordination. The measurements were also performed in 1,2-dimethoxyethane instead of acetonitrile with a five times lower dielectric constant, resulting in even larger difference in electron transfer rates between free base and Zn porphyrins. This suggests that the origin of the different coupling is indeed electrostatic in nature. The key finding of this work is that electronic coupling can be as significant contributor to electron transfer rates as the driving force even between similar molecular structures, hence redox active molecules should not be selected based on their free energy difference alone.

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“…Retardation of charge recombination increased the V oc , indicating that longer and larger molecules have a better blocking function. Further, a series of efficient carbazole-based sensitizers, JM1-JM3 76 and JK318-JK320, 77 were tested for DSSCs in the presence of Co-based redox mediators.…”

Section: Co-bipyridine-based Mediatorsmentioning

confidence: 99%

Transition metal complex redox shuttles for dye-sensitized solar cells

2015

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An important link exists between the selected molecular structure of a sensitizer and the employed shuttle electrolyte to achieve high conversion efficiency in dye-sensitized solar cells (DSSCs). So far, the most commonly used redox mediator is iodide/triiodide (I − /I 3 − ), which has shown advantages such as desirable kinetic properties and high carrier collection efficiencies. However, it has several disadvantages including a low redox potential, corrosion toward metal materials and competitive blue light absorption. In this respect, the transition metal complex electrolytes represent valuable alternatives to replace with traditional I − /I 3 − couples, which can overcome the drawbacks of I − /I 3 − electrolyte. In recent years, the best efficiency of DSSC was achieved by porphyrin-sensitized solar cells with transition metal complex-based redox electrolyte. In particular, in 2014, the Gratzel group published a record DSSC efficiency of 13 % by using a new porphyrin sensitizer with Co-polypyridyl-based electrolyte. Here, we plan the engineering of structure of new transition metal complex electrolyte and the design of molecular structure of sensitizer in touch. The main focus will be held on the correlation between photophysical and electrochemical properties of the metal complex mediators and their DSSC performances. This review provides an in-depth investigation on the exciting alternative electrolyte shuttle in DSSCs and their various advantages that are endowed with both high conversion efficiency and non-corrosive properties. Fig. 11 Device stability of [Fe(CN)6] 4-/3− mediated devices during light soaking with green (stars) and blue (pentagons) light. The performance parameters a) Voc b) Jsc c) FF and d) efficiency were measured at filtered (480 nm cut off) one sun AM 1.5 light. Reproduced with permission from ref. 85.

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Molecular engineering of carbazole-fluorene sensitizers for high open-circuit voltage DSSCs: Synthesis and performance comparison with iodine and cobalt electrolytes

Cited by 25 publications

References 32 publications

In silico designing of power conversion efficient organic lead dyes for solar cells using todays innovative approaches to assure renewable energy for future

In silico designing of power conversion efficient organic lead dyes for solar cells using todays innovative approaches to assure renewable energy for future

The Significant Effect of Electronic Coupling on Electron Transfer between Surface-Bound Porphyrins and Co^2+/3+ Complex Electrolytes

Transition metal complex redox shuttles for dye-sensitized solar cells

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Molecular engineering of carbazole-fluorene sensitizers for high open-circuit voltage DSSCs: Synthesis and performance comparison with iodine and cobalt electrolytes

Cited by 25 publications

References 32 publications

In silico designing of power conversion efficient organic lead dyes for solar cells using todays innovative approaches to assure renewable energy for future

In silico designing of power conversion efficient organic lead dyes for solar cells using todays innovative approaches to assure renewable energy for future

The Significant Effect of Electronic Coupling on Electron Transfer between Surface-Bound Porphyrins and Co2+/3+ Complex Electrolytes

Transition metal complex redox shuttles for dye-sensitized solar cells

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The Significant Effect of Electronic Coupling on Electron Transfer between Surface-Bound Porphyrins and Co^2+/3+ Complex Electrolytes