Two-State Intramolecular Charge Transfer (ICT) with 3,5-Dimethyl-4-(dimethylamino)benzonitrile (MMD) and Its Meta-Isomer mMMD. Ground State Amino Twist Not Essential for ICT

Sergey I. Druzhinin, Victor A. Galievsky, A. Demeter, Sergey A. Kovalenko, Tamara Senyushkina, Srinivas R. Dubbaka, Paul Knochel, Peter Mayer, Christian Grosse, Dietmar Stalke, Klaas A. Zachariasse

Research output: Contribution to journalArticle

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Abstract

From X-ray structure analysis, amino twist angles of 90.0° for 2,4-dimethyl-3-(dimethylamino)benzonitrile (mMMD), 82.7° for 4-(di-tert-butylamino)benzonitrile (DTABN), and 88.7° for 6-cyanobenzoquinuclidine (CBQ) are determined, all considerably larger than the 57.4° of 3,5-dimethyl-4-(dimethylamino)benzonitrile (MMD). This large twist leads to lengthening of the amino-phenyl bond, 143.5 pm (mMMD), 144.1 pm (DTABN), 144.6 pm (CBQ), and 141.4 pm (MMD), as compared with 136.5 pm for the planar 4-(dimethylamino)benzonitrile (DMABN). As a consequence, the electronic coupling between the amino and phenyl subgroups in mMMD, DTABN, CBQ, and MMD is much weaker than in DMABN, as seen from the strongly reduced molar absorption coefficients. The fluorescence spectrum of MMD in n-hexane at 25 °C consists of two emissions, from a locally excited (LE) and an intramolecular charge transfer (ICT) state, with a fluorescence quantum yield ratio Pdbl(ICT)/Pdbl(LE) of 12.8. In MeCN, a single ICT emission is found. With mMMD in n-hexane, in contrast, only LE fluorescence is observed, whereas the spectrum in MeCN originates from the ICT state. These differences are also seen from the half-widths of the overall fluorescence bands, which in n-hexane are larger for MMD than for mMMD, decreasing with solvent polarity for MMD and increasing for mMMD, reflecting the disappearance of LE and the onset of ICT in the overall spectra, respectively. From solvatochromic measurements the dipole moments μe(ICT) of MMD (16 D) and mMMD (15 D) are obtained. Femtosecond excited state absorption (ESA) spectra at 22 °C, together with the dual (LE + ICT) fluorescence, reveal that MMD in n-hexane undergoes a reversible LE ⇄ ICT reaction, with LE as the precursor, with a forward rate constant ka = 5.6 × 1012 s-1 and a back-reaction kd ∼ 0.05 × 1012 s-1. With MMD in the strongly polar solvent MeCN, ICT is faster: ka = 10 × 1012 s-1. In the case of mMMD in n-hexane, the ESA spectra show that ICT does not take place, contrary to MeCN, in which ka = 2.5 × 1012 s-1. The ICT reactions with MMD and mMMD are much faster than that of the parent compound DMABN in MeCN, with ka = 0.24 × 1012 s-1. Because of the very short ICT reaction times of 180 fs (MMD, n-hexane), 100 fs (MMD, MeCN), and 400 fs (mMMD, MeCN), it is clear that the picosecond fluorescence decays of these systems appear to be single exponential, due to the insufficient time resolution of 3 ps. It is concluded that the faster LE ICT reaction of MMD as compared with DMABN (ka = 0.24 × 1012 s-1 in MeCN) is caused by a smaller energy gap E(S1,S2) between the lowest singlet excited states and not by the large amino twist angle. Similarly, the larger E(S1,S2) of mMMD as compared with MMD is held responsible for its smaller ICT efficiency (no reaction in n-hexane).

Original languageEnglish
Pages (from-to)11820-11836
Number of pages17
JournalJournal of Physical Chemistry A
Volume119
Issue number49
DOIs
Publication statusPublished - Dec 10 2015

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Isomers
Ground state
Charge transfer
isomers
charge transfer
ground state
Fluorescence
fluorescence
Excited states
benzonitrile
Absorption spectra
excitation
absorption spectra
Dipole moment
Quantum yield
subgroups
n-hexane
reaction time
Rate constants
absorptivity

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Two-State Intramolecular Charge Transfer (ICT) with 3,5-Dimethyl-4-(dimethylamino)benzonitrile (MMD) and Its Meta-Isomer mMMD. Ground State Amino Twist Not Essential for ICT. / Druzhinin, Sergey I.; Galievsky, Victor A.; Demeter, A.; Kovalenko, Sergey A.; Senyushkina, Tamara; Dubbaka, Srinivas R.; Knochel, Paul; Mayer, Peter; Grosse, Christian; Stalke, Dietmar; Zachariasse, Klaas A.

In: Journal of Physical Chemistry A, Vol. 119, No. 49, 10.12.2015, p. 11820-11836.

Research output: Contribution to journalArticle

Druzhinin, SI, Galievsky, VA, Demeter, A, Kovalenko, SA, Senyushkina, T, Dubbaka, SR, Knochel, P, Mayer, P, Grosse, C, Stalke, D & Zachariasse, KA 2015, 'Two-State Intramolecular Charge Transfer (ICT) with 3,5-Dimethyl-4-(dimethylamino)benzonitrile (MMD) and Its Meta-Isomer mMMD. Ground State Amino Twist Not Essential for ICT', Journal of Physical Chemistry A, vol. 119, no. 49, pp. 11820-11836. https://doi.org/10.1021/acs.jpca.5b09368
Druzhinin, Sergey I. ; Galievsky, Victor A. ; Demeter, A. ; Kovalenko, Sergey A. ; Senyushkina, Tamara ; Dubbaka, Srinivas R. ; Knochel, Paul ; Mayer, Peter ; Grosse, Christian ; Stalke, Dietmar ; Zachariasse, Klaas A. / Two-State Intramolecular Charge Transfer (ICT) with 3,5-Dimethyl-4-(dimethylamino)benzonitrile (MMD) and Its Meta-Isomer mMMD. Ground State Amino Twist Not Essential for ICT. In: Journal of Physical Chemistry A. 2015 ; Vol. 119, No. 49. pp. 11820-11836.
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title = "Two-State Intramolecular Charge Transfer (ICT) with 3,5-Dimethyl-4-(dimethylamino)benzonitrile (MMD) and Its Meta-Isomer mMMD. Ground State Amino Twist Not Essential for ICT",
abstract = "From X-ray structure analysis, amino twist angles of 90.0° for 2,4-dimethyl-3-(dimethylamino)benzonitrile (mMMD), 82.7° for 4-(di-tert-butylamino)benzonitrile (DTABN), and 88.7° for 6-cyanobenzoquinuclidine (CBQ) are determined, all considerably larger than the 57.4° of 3,5-dimethyl-4-(dimethylamino)benzonitrile (MMD). This large twist leads to lengthening of the amino-phenyl bond, 143.5 pm (mMMD), 144.1 pm (DTABN), 144.6 pm (CBQ), and 141.4 pm (MMD), as compared with 136.5 pm for the planar 4-(dimethylamino)benzonitrile (DMABN). As a consequence, the electronic coupling between the amino and phenyl subgroups in mMMD, DTABN, CBQ, and MMD is much weaker than in DMABN, as seen from the strongly reduced molar absorption coefficients. The fluorescence spectrum of MMD in n-hexane at 25 °C consists of two emissions, from a locally excited (LE) and an intramolecular charge transfer (ICT) state, with a fluorescence quantum yield ratio Pdbl(ICT)/Pdbl(LE) of 12.8. In MeCN, a single ICT emission is found. With mMMD in n-hexane, in contrast, only LE fluorescence is observed, whereas the spectrum in MeCN originates from the ICT state. These differences are also seen from the half-widths of the overall fluorescence bands, which in n-hexane are larger for MMD than for mMMD, decreasing with solvent polarity for MMD and increasing for mMMD, reflecting the disappearance of LE and the onset of ICT in the overall spectra, respectively. From solvatochromic measurements the dipole moments μe(ICT) of MMD (16 D) and mMMD (15 D) are obtained. Femtosecond excited state absorption (ESA) spectra at 22 °C, together with the dual (LE + ICT) fluorescence, reveal that MMD in n-hexane undergoes a reversible LE ⇄ ICT reaction, with LE as the precursor, with a forward rate constant ka = 5.6 × 1012 s-1 and a back-reaction kd ∼ 0.05 × 1012 s-1. With MMD in the strongly polar solvent MeCN, ICT is faster: ka = 10 × 1012 s-1. In the case of mMMD in n-hexane, the ESA spectra show that ICT does not take place, contrary to MeCN, in which ka = 2.5 × 1012 s-1. The ICT reactions with MMD and mMMD are much faster than that of the parent compound DMABN in MeCN, with ka = 0.24 × 1012 s-1. Because of the very short ICT reaction times of 180 fs (MMD, n-hexane), 100 fs (MMD, MeCN), and 400 fs (mMMD, MeCN), it is clear that the picosecond fluorescence decays of these systems appear to be single exponential, due to the insufficient time resolution of 3 ps. It is concluded that the faster LE ICT reaction of MMD as compared with DMABN (ka = 0.24 × 1012 s-1 in MeCN) is caused by a smaller energy gap E(S1,S2) between the lowest singlet excited states and not by the large amino twist angle. Similarly, the larger E(S1,S2) of mMMD as compared with MMD is held responsible for its smaller ICT efficiency (no reaction in n-hexane).",
author = "Druzhinin, {Sergey I.} and Galievsky, {Victor A.} and A. Demeter and Kovalenko, {Sergey A.} and Tamara Senyushkina and Dubbaka, {Srinivas R.} and Paul Knochel and Peter Mayer and Christian Grosse and Dietmar Stalke and Zachariasse, {Klaas A.}",
year = "2015",
month = "12",
day = "10",
doi = "10.1021/acs.jpca.5b09368",
language = "English",
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TY - JOUR

T1 - Two-State Intramolecular Charge Transfer (ICT) with 3,5-Dimethyl-4-(dimethylamino)benzonitrile (MMD) and Its Meta-Isomer mMMD. Ground State Amino Twist Not Essential for ICT

AU - Druzhinin, Sergey I.

AU - Galievsky, Victor A.

AU - Demeter, A.

AU - Kovalenko, Sergey A.

AU - Senyushkina, Tamara

AU - Dubbaka, Srinivas R.

AU - Knochel, Paul

AU - Mayer, Peter

AU - Grosse, Christian

AU - Stalke, Dietmar

AU - Zachariasse, Klaas A.

PY - 2015/12/10

Y1 - 2015/12/10

N2 - From X-ray structure analysis, amino twist angles of 90.0° for 2,4-dimethyl-3-(dimethylamino)benzonitrile (mMMD), 82.7° for 4-(di-tert-butylamino)benzonitrile (DTABN), and 88.7° for 6-cyanobenzoquinuclidine (CBQ) are determined, all considerably larger than the 57.4° of 3,5-dimethyl-4-(dimethylamino)benzonitrile (MMD). This large twist leads to lengthening of the amino-phenyl bond, 143.5 pm (mMMD), 144.1 pm (DTABN), 144.6 pm (CBQ), and 141.4 pm (MMD), as compared with 136.5 pm for the planar 4-(dimethylamino)benzonitrile (DMABN). As a consequence, the electronic coupling between the amino and phenyl subgroups in mMMD, DTABN, CBQ, and MMD is much weaker than in DMABN, as seen from the strongly reduced molar absorption coefficients. The fluorescence spectrum of MMD in n-hexane at 25 °C consists of two emissions, from a locally excited (LE) and an intramolecular charge transfer (ICT) state, with a fluorescence quantum yield ratio Pdbl(ICT)/Pdbl(LE) of 12.8. In MeCN, a single ICT emission is found. With mMMD in n-hexane, in contrast, only LE fluorescence is observed, whereas the spectrum in MeCN originates from the ICT state. These differences are also seen from the half-widths of the overall fluorescence bands, which in n-hexane are larger for MMD than for mMMD, decreasing with solvent polarity for MMD and increasing for mMMD, reflecting the disappearance of LE and the onset of ICT in the overall spectra, respectively. From solvatochromic measurements the dipole moments μe(ICT) of MMD (16 D) and mMMD (15 D) are obtained. Femtosecond excited state absorption (ESA) spectra at 22 °C, together with the dual (LE + ICT) fluorescence, reveal that MMD in n-hexane undergoes a reversible LE ⇄ ICT reaction, with LE as the precursor, with a forward rate constant ka = 5.6 × 1012 s-1 and a back-reaction kd ∼ 0.05 × 1012 s-1. With MMD in the strongly polar solvent MeCN, ICT is faster: ka = 10 × 1012 s-1. In the case of mMMD in n-hexane, the ESA spectra show that ICT does not take place, contrary to MeCN, in which ka = 2.5 × 1012 s-1. The ICT reactions with MMD and mMMD are much faster than that of the parent compound DMABN in MeCN, with ka = 0.24 × 1012 s-1. Because of the very short ICT reaction times of 180 fs (MMD, n-hexane), 100 fs (MMD, MeCN), and 400 fs (mMMD, MeCN), it is clear that the picosecond fluorescence decays of these systems appear to be single exponential, due to the insufficient time resolution of 3 ps. It is concluded that the faster LE ICT reaction of MMD as compared with DMABN (ka = 0.24 × 1012 s-1 in MeCN) is caused by a smaller energy gap E(S1,S2) between the lowest singlet excited states and not by the large amino twist angle. Similarly, the larger E(S1,S2) of mMMD as compared with MMD is held responsible for its smaller ICT efficiency (no reaction in n-hexane).

AB - From X-ray structure analysis, amino twist angles of 90.0° for 2,4-dimethyl-3-(dimethylamino)benzonitrile (mMMD), 82.7° for 4-(di-tert-butylamino)benzonitrile (DTABN), and 88.7° for 6-cyanobenzoquinuclidine (CBQ) are determined, all considerably larger than the 57.4° of 3,5-dimethyl-4-(dimethylamino)benzonitrile (MMD). This large twist leads to lengthening of the amino-phenyl bond, 143.5 pm (mMMD), 144.1 pm (DTABN), 144.6 pm (CBQ), and 141.4 pm (MMD), as compared with 136.5 pm for the planar 4-(dimethylamino)benzonitrile (DMABN). As a consequence, the electronic coupling between the amino and phenyl subgroups in mMMD, DTABN, CBQ, and MMD is much weaker than in DMABN, as seen from the strongly reduced molar absorption coefficients. The fluorescence spectrum of MMD in n-hexane at 25 °C consists of two emissions, from a locally excited (LE) and an intramolecular charge transfer (ICT) state, with a fluorescence quantum yield ratio Pdbl(ICT)/Pdbl(LE) of 12.8. In MeCN, a single ICT emission is found. With mMMD in n-hexane, in contrast, only LE fluorescence is observed, whereas the spectrum in MeCN originates from the ICT state. These differences are also seen from the half-widths of the overall fluorescence bands, which in n-hexane are larger for MMD than for mMMD, decreasing with solvent polarity for MMD and increasing for mMMD, reflecting the disappearance of LE and the onset of ICT in the overall spectra, respectively. From solvatochromic measurements the dipole moments μe(ICT) of MMD (16 D) and mMMD (15 D) are obtained. Femtosecond excited state absorption (ESA) spectra at 22 °C, together with the dual (LE + ICT) fluorescence, reveal that MMD in n-hexane undergoes a reversible LE ⇄ ICT reaction, with LE as the precursor, with a forward rate constant ka = 5.6 × 1012 s-1 and a back-reaction kd ∼ 0.05 × 1012 s-1. With MMD in the strongly polar solvent MeCN, ICT is faster: ka = 10 × 1012 s-1. In the case of mMMD in n-hexane, the ESA spectra show that ICT does not take place, contrary to MeCN, in which ka = 2.5 × 1012 s-1. The ICT reactions with MMD and mMMD are much faster than that of the parent compound DMABN in MeCN, with ka = 0.24 × 1012 s-1. Because of the very short ICT reaction times of 180 fs (MMD, n-hexane), 100 fs (MMD, MeCN), and 400 fs (mMMD, MeCN), it is clear that the picosecond fluorescence decays of these systems appear to be single exponential, due to the insufficient time resolution of 3 ps. It is concluded that the faster LE ICT reaction of MMD as compared with DMABN (ka = 0.24 × 1012 s-1 in MeCN) is caused by a smaller energy gap E(S1,S2) between the lowest singlet excited states and not by the large amino twist angle. Similarly, the larger E(S1,S2) of mMMD as compared with MMD is held responsible for its smaller ICT efficiency (no reaction in n-hexane).

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