TY - JOUR
T1 - Enhanced fluorescence of phthalimide compounds induced by the incorporation of electron-donating alicyclic amino groups
AU - Orita, Ryoji
AU - Franckevičius, Marius
AU - Vyšniauskas, Aurimas
AU - Gulbinas, Vidmantas
AU - Sugiyama, Haruki
AU - Uekusa, Hidehiro
AU - Kanosue, Kenta
AU - Ishige, Ryohei
AU - Ando, Shinji
N1 - Funding Information:
This work was partly financed by Grants-in-Aid for Scientific Research, Japan Society for the Promotion of Science (25288096, 15K13782, 17H03112, 17K05745), and the Bilateral Joint Japan–Lithuanian Research Project by the Japan Society for the Promotion of Science and the Lithuanian Research Council (LJB-17-007). The authors wish to thank Ms Mayuko Nara at Tokyo Institute of Technology for her help in measuring DTA data of imide compounds.
Publisher Copyright:
© 2018 the Owner Societies.
PY - 2018
Y1 - 2018
N2 - Due to their high thermal and environmental stability, polyimides (PIs) are one of the most attractive candidates for novel highly fluorescent polymers, though photophysical studies of PIs are challenging owing to their poor solubility in common solvents. To overcome these problems, we have synthesized and examined a series of low molecular weight model imide compounds: substituted N-cyclohexylphthalimides with alicyclic amino groups at the 3 or 4-positions of the benzene rings (x-NHPIs). Their photophysical properties were systematically investigated by steady-state UV/Visible absorption, fluorescence, and time-resolved fluorescence techniques. In solution, unsubstituted N-cyclohexylphthalimide (NHPI) showed almost no emission, while x-NHPIs exhibited enhanced fluorescence emission depending on the solvent polarity. Analysis of the solvatochromism of the x-NHPIs via Lippert-Mataga plots indicated the generation of large dipole moments in the excited singlet states originating from the intramolecular charge-transfer (ICT) states. The significant difference in the fluorescence quantum yields (Φ) between the 3-substituted (3Pi and 3Pyr) and 4-substituted NHPIs (4Pi and 4Pyr) strongly suggests that the former form a twisted ICT (TICT) state, whereas the latter form a planar ICT (PICT) state when excited. 4-Substituted NHPIs also show high fluorescence yields in the crystalline state. A particularly large Φ value was obtained for the 4Pi crystal, which we explain by the large intermolecular distances and the arrangement of molecules minimizing intermolecular interactions as well as the small non-radiative deactivation rate. These facts clearly demonstrate that the introduction of an alicyclic amino group into NHPI at the 4-position enhances the fluorescence quantum yields significantly, which suggests a new pathway for the development of novel, highly fluorescent PIs.
AB - Due to their high thermal and environmental stability, polyimides (PIs) are one of the most attractive candidates for novel highly fluorescent polymers, though photophysical studies of PIs are challenging owing to their poor solubility in common solvents. To overcome these problems, we have synthesized and examined a series of low molecular weight model imide compounds: substituted N-cyclohexylphthalimides with alicyclic amino groups at the 3 or 4-positions of the benzene rings (x-NHPIs). Their photophysical properties were systematically investigated by steady-state UV/Visible absorption, fluorescence, and time-resolved fluorescence techniques. In solution, unsubstituted N-cyclohexylphthalimide (NHPI) showed almost no emission, while x-NHPIs exhibited enhanced fluorescence emission depending on the solvent polarity. Analysis of the solvatochromism of the x-NHPIs via Lippert-Mataga plots indicated the generation of large dipole moments in the excited singlet states originating from the intramolecular charge-transfer (ICT) states. The significant difference in the fluorescence quantum yields (Φ) between the 3-substituted (3Pi and 3Pyr) and 4-substituted NHPIs (4Pi and 4Pyr) strongly suggests that the former form a twisted ICT (TICT) state, whereas the latter form a planar ICT (PICT) state when excited. 4-Substituted NHPIs also show high fluorescence yields in the crystalline state. A particularly large Φ value was obtained for the 4Pi crystal, which we explain by the large intermolecular distances and the arrangement of molecules minimizing intermolecular interactions as well as the small non-radiative deactivation rate. These facts clearly demonstrate that the introduction of an alicyclic amino group into NHPI at the 4-position enhances the fluorescence quantum yields significantly, which suggests a new pathway for the development of novel, highly fluorescent PIs.
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U2 - 10.1039/c8cp01999a
DO - 10.1039/c8cp01999a
M3 - Article
C2 - 29850675
AN - SCOPUS:85048559109
VL - 20
SP - 16033
EP - 16044
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
SN - 1463-9076
IS - 23
ER -