Molecular engineering of thia-bridged triphenylamine heterohelicenes as novel organic dyes for dye-sensitized solar cells

Kim, Chulwoo; Choi, Hyunbong; Paek, Sanghyun; Kim, Jeum‐Jong; Song, Kihyung; Kang, Moon‐Sung; Ko, Jaejung

doi:10.1016/j.jphotochem.2011.09.020

Cited by 11 publications

(5 citation statements)

References 46 publications

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“…The latter three were also chosen to provide an additional IR-sensitive label as an independent probe for electronic changes at the TAA site. The corresponding ethynyl-substituted amines (4-HCCC 6 H 4 )N(C 6 H 4 -4-R) 2 were prepared according to literature procedures. ,− Details of the syntheses and characterization can be found in the Supporting Information (SI; see also Figures S1–S3). The target complexes were then obtained in high to quantitative yields by the regio- and stereoselective cis insertion of the ethynyl function into the Ru–H bond of HRu(CO)Cl(P i Pr 3 ) 2 (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

Manipulation and Assessment of Charge and Spin Delocalization in Mixed-Valent Triarylamine–Vinylruthenium Conjugates

Hassenrück

Winter

2017

Inorg. Chem.

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Triarylamine-vinylruthenium conjugates (4-RCH)N{CH-4-CH═CHRu(CO)Cl(PPr)}, with R = CHO (1-CHO), C(═O)Me (1-Ac), COOMe (1-E), and Me (1-Me), have been prepared and investigated in their neutral, mono- and dioxidized states by cyclic voltammetry, IR, and UV/vis/near-infrared spectroelectrochemistry, electron paramagnetic resonance spectroscopy, and quantum-chemical calculations. Electron-withdrawing substituents at the triarylamine moiety shift the charge and spin density toward the more electron-rich vinylruthenium site in comparison to the 4-OMe-substituted triarylamine-vinylruthenium conjugate 1-OMe. A more asymmetric charge distribution changes the intense vibrationally structured intervalence charge-transfer (IVCT) band of completely delocalized, mixed-valent (MV) 1-OMe to a weaker, highly asymmetric, nonsolvatochromic band with significantly smaller bandwidth at the low-energy side. The temperature dependence of the IVCT band of the formyl derivative 1-CHO proves that vibrational coupling of the IVCT transition to a symmetrical vibration is the underlying reason for band skewing. All of our results indicate that the MV radical cations remain electronically strongly coupled despite an increasingly stronger bias of the highest occupied molecular orbital to the vinylruthenium entity. Moreover, the dications of these complexes were found to be paramagnetic, which makes them rare examples of compounds that combine strong electronic coupling in the cationic MV state with paramagnetism of the dications.

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Section: Resultsmentioning

confidence: 99%

Manipulation and Assessment of Charge and Spin Delocalization in Mixed-Valent Triarylamine–Vinylruthenium Conjugates

Hassenrück

Winter

2017

Inorg. Chem.

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Section: Resultsmentioning

confidence: 99%

“…Planarizing the triarylamine donor through two sulfur bridges reported worse photovoltaic performance compared to a “free” triarylamine reference dye. 30 To study the effect of planarizing the triarylamine donor with heteroatom bridges, we report herein five novel dyes with moderately sized π-spacers based on the common triarylamine donor motif, see Figure 1 a. The degree of planarization on these donors varies from the “free” triarylamine motif to the single planarization of the phenothiazine motifs and all the way to the double phenoxazine motif.…”

Section: Introductionmentioning

confidence: 99%

“…40 The fully planarized double phenoxazine donor, seen for POZPOZ-Th, has not previously been reported. However, some double phenothiazine helicene analogues have been used in dyes for DSSC by Kim et al 30 To assess the planarity of the different donors reported herein, we use previously reported crystallographic data of the simpler compounds triphenylamine, 32 2-chloro-10-phenylphenothiazine, 31 and benzo [5,6][1,4]oxazino [2,3,4-kl]phenoxazine. 33 The three central rings of the "free" triarylamine donor (TAA-Th and TAA-Fu) are all expected to be 69−76°out of plane with each other.…”

Section: ■ Introductionmentioning

confidence: 99%

“…There are studies on planarizing the triarylamine donor through bridging with methylene and diarylmethylene compared to the “free” triarylamine. Planarizing the triarylamine donor through two sulfur bridges reported worse photovoltaic performance compared to a “free” triarylamine reference dye . To study the effect of planarizing the triarylamine donor with heteroatom bridges, we report herein five novel dyes with moderately sized π-spacers based on the common triarylamine donor motif, see Figure a.…”

Section: Introductionmentioning

confidence: 99%

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Synthetic Efforts to Investigate the Effect of Planarizing the Triarylamine Geometry in Dyes for Dye-Sensitized Solar Cells

et al. 2022

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The geometry of a dye for dye-sensitized solar cells (DSSCs) has a major impact on its optical and electronic properties. The dye structure also dictates the packing properties and how well the dye insulates the metal–oxide surface from oxidants in the electrolyte. The aim of this work is to investigate the effect of planarizing the geometry of the common triarylamine donor, frequently used in dyes for DSSC. Five novel dyes were designed and prepared; two employ conventional triarylamine donors with thiophene and furan π-spacers, two dyes have had their donors planarized through one sulfur bridge (making two distinct phenothiazine motifs), and the final dye has been planarized by forming a double phenoxazine. The synthesis of these model dyes proved to be quite challenging, and each required specially designed total syntheses. We demonstrate that the planarization of the triarylamine donor can have different effects. When planarization was achieved by a 3,7-phenothiazine and double phenoxazine structures, improved absorption properties were noted, and a panchromatic absorption was achieved by the latter. However, an incorrect linking of donor and acceptor moieties has the opposite effect. Further, electrochemical impedance spectroscopy revealed clear differences in charge recombination depending on the structure of the dye. A drawback of planarized dyes in relation to DSSC is their low oxidation potentials. The best photovoltaic performance was achieved by 3,7-phenothazine with furan as a π-spacer, which produces a power conversion efficiency of 5.2% ( J sc = 8.8 mA cm –2 , V oc = 838 mV, FF = 0.70).

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A Lewis Base Hydrogen Bond Donor (LB/HBD) Organocatalytic Approach to Dithiabridged Triarylamine Hetero[4]helicenes

et al. 2023

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N-thiophthalimido-arylphenothiazines 2 and triarylamines 3 can be converted to dithiabridged triarylamine hetero[4]helicenes 1 using catalytic amounts of chalcogen substituted Lewis Bases and hexafluoro isopropanol as hydrogen bond donor. The procedure occurs under mild reaction conditions and gives good yields avoiding the use of excesses of Lewis Acids as previously reported. A preliminary study about the possibility to control the M and P absolute stereochemistry of helicenes 1 using enantiopure sulfur containing LBs from the natural chiral pool is also reported.

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Molecular engineering of thia-bridged triphenylamine heterohelicenes as novel organic dyes for dye-sensitized solar cells

Cited by 11 publications

References 46 publications

Manipulation and Assessment of Charge and Spin Delocalization in Mixed-Valent Triarylamine–Vinylruthenium Conjugates

Manipulation and Assessment of Charge and Spin Delocalization in Mixed-Valent Triarylamine–Vinylruthenium Conjugates

Synthetic Efforts to Investigate the Effect of Planarizing the Triarylamine Geometry in Dyes for Dye-Sensitized Solar Cells

A Lewis Base Hydrogen Bond Donor (LB/HBD) Organocatalytic Approach to Dithiabridged Triarylamine Hetero[4]helicenes

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