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Twisted Intramolecu...
Twisted Intramolecular Charge Transfer (TICT) Controlled by Dimerization : An Overlooked Piece of the TICT Puzzle
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- El-Zohry, Ahmed M. (författare)
- Uppsala universitet,Stockholms universitet,Fysikum,Uppsala University, Sweden,Fysikalisk kemi,Stockholm Univ, Dept Phys, AlbaNova Univ Ctr, SE-10691 Stockholm, Sweden.
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- Orabi, Esam A. (författare)
- Univ Manitoba, Dept Chem, Winnipeg, MB R3T 2N2, Canada.
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- Karlsson, Karl Martin, 1981- (författare)
- KTH,Tillämpad fysikalisk kemi,KTH Royal Inst Technol, Appl Phys Chem, SE-10044 Stockholm, Sweden.
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- Zietz, Burkhard (författare)
- Uppsala universitet,Fysikalisk kemi
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(creator_code:org_t)
- 2021-04-05
- 2021
- Engelska.
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Ingår i: Journal of Physical Chemistry A. - : American Chemical Society (ACS). - 1089-5639 .- 1520-5215. ; 125:14, s. 2885-2894
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Abstract
Ämnesord
Stäng
- Organic dyes have shown high efficiencies in solar cells, which is mainly attributed to the push-pull strategy present in such dyes upon attaching to the semiconductor surfaces. We deeply studied the fundamental photophysical properties of cyanoacrylic dyes, mostly the L1 dye, and found unique emission properties that depend on many factors such as the solvent polarity and the concentration of the dye and could present a complete emission picture about this family of dyes. The L1 dye shows an intramolecular charge transfer (ICT) emission state at low concentrations (approximately nanomolar scale) and shows a twisted intramolecular charge transfer (TICT) emission state in specific solvents upon increasing the concentration to the micromolar scale. Moreover, the associated emission lifetimes of the ICT and TICT states of the L1 dye depend on solvent basicity, highlighting the role of hydrogen bond formation on controlling such states. Density functional theory calculations are performed to gain insight into the photophysical properties of the dye and revealed that H-bonding between the carboxylic groups triggers the dimerization at low concentrations. Using femtosecond transient absorption, we assigned the rate of TICT formation to be in the range (160-650 fs)(-1), depending on the size of the studied cyanoacrylic dye. Therefore, we add herein a new dimension for controlling the formation of the TICT state, in addition to the solvent polarity and acceptor strength parameters. These findings are not limited to the studied dyes, and we expect that numerous organic carboxylic acids dyes show similar properties.
Ämnesord
- NATURVETENSKAP -- Kemi -- Fysikalisk kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences -- Physical Chemistry (hsv//eng)
- NATURVETENSKAP -- Kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences (hsv//eng)
- NATURVETENSKAP -- Fysik (hsv//swe)
- NATURAL SCIENCES -- Physical Sciences (hsv//eng)
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