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Electronic relaxation dynamics of PCDA-PDA studied by transient absorption spectroscopy

Title
Electronic relaxation dynamics of PCDA-PDA studied by transient absorption spectroscopy
Authors
Joung, Joonyoung F.Baek, JunwooKim, YoungseoLee, SongyiKim, Myung HwaYoon, JuyoungPark, Sungnam
Ewha Authors
윤주영김명화
SCOPUS Author ID
윤주영scopus; 김명화scopus
Issue Date
2016
Journal Title
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
ISSN
1463-9076JCR Link1463-9084JCR Link
Citation
vol. 18, no. 33, pp. 23096 - 23104
Publisher
ROYAL SOC CHEMISTRY
Indexed
SCI; SCIE; SCOPUS WOS scopus
Abstract
Photo-curable polymers originating from 10,12-pentacosadiynoic acid (PCDA-PDA) are commonly used polydiacetylenes (PDAs). PCDA-PDA exhibits thermochromic properties undergoing a unique colorimetric transition from blue to red as the temperature is increased from low to high. In this work, we have carefully studied the temperature-dependent optical properties of PCDA-PDA by using UV-visible absorption, FTIR, Raman, and transient absorption (TA) spectroscopy in combination with quantum chemical calculations. Temperature-dependent UV-visible absorption spectra indicate that PCDA-PDA exhibits reversible thermochromic properties up to 60 degrees C and its thermochromic properties become irreversible above 60 degrees C. Such distinct thermochromic properties are also manifested in TA signals so that the electronically excited PCDA-PDA relaxes to the ground state via an intermediate state at 20 degrees C (blue form) but it relaxes directly back to the ground state at 80 degrees C (red form). The electronic relaxation dynamics of PCDA-PDA are comprehensively analyzed based on different kinetic models by using the global fitting analysis method. The intermediate state in the blue form of PCDA-PDA is clearly found to be responsible for fluorescence quenching. FTIR and Raman spectroscopy and quantum chemical calculations confirm that the H-bonds between the carboxylic acid groups in PCDA-PDA are broken at high temperatures leading to an irreversible structural change of PCDA-PDA.
DOI
10.1039/c6cp03858a
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자연과학대학 > 화학·나노과학전공 > Journal papers
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