Fast time-resolved IR studies of the excited states of co-ordination compound: direct observation of intramolecular charge transfer

Glyn, Paul; George, Michael W.; Hodges, P. Michael; Turner, James J.

doi:10.1039/c39890001655

Cited by 57 publications

(52 citation statements)

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“…[Re(CO) 3 (bpy)Cl] (bpy ¼ C 10 H 6 N 2 ) and its related compounds have been extensively studied [14][15][16][17] in solution phase and the vibrational spectra of the ground-and excitedstate spectral assignments are well established; for this reason the compound was selected as a test sample for the solid-state development of the time-resolved IR technique.…”

Section: Resultsmentioning

confidence: 99%

A Time-Resolved Infrared Vibrational Spectroscopic Study of the Photo-Dynamics of Crystalline Materials

Towrie

Parker²,

Ronayne³

et al. 2009

Appl Spectrosc

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Time-resolved infrared vibrational spectroscopy is a structurally sensitive probe of the excited-state properties of matter. The technique has found many applications in the study of molecules in dilute solution phase but has rarely been applied to crystalline samples. We report on the use of a sensitive pump-probe time-resolved infrared spectrometer and sample handling techniques for studies of the ultrafast excited-state dynamics of crystalline materials. The charge transfer excited states of crystalline metal carbonyls and the proton transfer of dihydroxyquinones are presented and compared with the solution phase.

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Section: Resultsmentioning

confidence: 99%

A Time-Resolved Infrared Vibrational Spectroscopic Study of the Photo-Dynamics of Crystalline Materials

Towrie

Parker²,

Ronayne³

et al. 2009

Appl Spectrosc

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“…In addition, a weak feature is seen at about 1870 cm À1 (M), which is indicative of a very small population of a 3 Figure S1). The large upward shift of the bands K and L from their respective ground state positions shows [2,50,56,[61][62][63][64][65][66] that they belong to the 3 , respectively. It is also larger than was observed [50] for an analogous complex [Re(Cl)(CO) 3 (4,4'-bipyridine) 2 ]: +30 cm À1 in CH 2 Cl 2 .…”

Section: Spectrum Of [Rea C H T U N G T R E N N U N G (Medpe + )(Co) mentioning

confidence: 97%

Ultrafast Excited State Dynamics Controlling Photochemical Isomerization of N‐Methyl‐4‐[trans‐2‐(4‐pyridyl)ethenyl]pyridinium Coordinated to a {Re^I(CO)₃(2,2′‐bipyridine)} Chromophore

Hartl

Matousek

Towrie

et al. 2008

Chemistry A European J

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Two multifunctional photoactive complexes [Re(Cl)(CO)(3)(MeDpe(+))(2)](2+) and [Re(MeDpe(+))(CO)(3)(bpy)](2+) (MeDpe(+)=N-methyl-4-[trans-2-(4-pyridyl)ethenyl]pyridinium, bpy=2,2'-bipyridine) were synthesized, characterized, and their redox and photonic properties were investigated by cyclic voltammetry; ultraviolet-visible-infrared (UV/Vis/IR) spectroelectrochemistry, stationary UV/Vis and resonance Raman spectroscopy; photolysis; picosecond time-resolved absorption spectroscopy in the visible and infrared regions; and time-resolved resonance Raman spectroscopy. The first reduction step of either complex occurs at about -1.1 V versus Fc/Fc(+) and is localized at MeDpe(+). Reduction alone does not induce a trans-->cis isomerization of MeDpe(+). [Re(Cl)(CO)(3)(MeDpe(+))(2)](2+) is photostable, while [Re(MeDpe(+))(CO)(3)(bpy)](2+) and free MeDpe(+) isomerize under near-UV irradiation. The lowest excited state of [Re(Cl)(CO)(3)(MeDpe(+))(2)](2+) has been identified as the Re(Cl)(CO)(3)-->MeDpe(+ 3)MLCT (MLCT=metal-to-ligand charge transfer), decaying directly to the ground state with lifetimes of approximately 42 (73 %) and approximately 430 ps (27 %). Optical excitation of [Re(MeDpe(+))(CO)(3)(bpy)](2+) leads to population of Re(CO)(3)-->MeDpe(+) and Re(CO)(3)-->bpy (3)MLCT states, from which a MeDpe(+) localized intraligand (3)pipi* excited state ((3)IL) is populated with lifetimes of approximately 0.6 and approximately 10 ps, respectively. The (3)IL state undergoes a approximately 21 ps internal rotation, which eventually produces the cis isomer on a much longer timescale. The different excited-state behavior of the two complexes and the absence of thermodynamically favorable interligand electron transfer in excited [Re(MeDpe(+))(CO)(3)(bpy)](2+) reflect the fine energetic balance between excited states of different orbital origin, which can be tuned by subtle structural variations. The complex [Re(MeDpe(+))(CO)(3)(bpy)](2+) emerges as a prototypical, multifunctional species with complementary redox and photonic behavior.

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“…The species formed is characteristic of the production of a Re-diimine 3 MLCT excited state where the ν(CO) bands shift up in energy due to the oxidation of the Re center ([Re]*-[NiFe 2 ]). 24 Such behavior has been reported for numerous [ReCl(CO) 3 (diimine)] 3 MLCT excited states, and the shift in the ν(CO) bands to higher wavenumber has been well-documented. 25 Following photolysis, the 3 MLCT bands decay (τ = 20 ± 1 ns, Figure 7 d, blue dots), and the parent bands reform ( Figure 7 d, black dots).…”

Section: Resultsmentioning

confidence: 58%

Synthesis and Photophysical Study of a [NiFe] Hydrogenase Biomimetic Compound Covalently Linked to a Re-diimine Photosensitizer

et al. 2015

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The synthesis, photophysics, and photochemistry of a linked dyad ([Re]-[NiFe2]) containing an analogue ([NiFe2]) of the active site of [NiFe] hydrogenase, covalently bound to a Re-diimine photosensitizer ([Re]), are described. Following excitation, the mechanisms of electron transfer involving the [Re] and [NiFe2] centers and the resulting decomposition were investigated. Excitation of the [Re] center results in the population of a diimine-based metal-to-ligand charge transfer excited state. Reductive quenching by NEt3 produces the radically reduced form of [Re], [Re]− (kq = 1.4 ± 0.1 × 107 M–1 s–1). Once formed, [Re]− reduces the [NiFe2] center to [NiFe2]−, and this reduction was followed using time-resolved infrared spectroscopy. The concentration dependence of the electron transfer rate constants suggests that both inter- and intramolecular electron transfer pathways are involved, and the rate constants for these processes have been estimated (kinter = 5.9 ± 0.7 × 108 M–1 s–1, kintra = 1.5 ± 0.1 × 105 s–1). For the analogous bimolecular system, only intermolecular electron transfer could be observed (kinter = 3.8 ± 0.5 × 109 M–1 s–1). Fourier transform infrared spectroscopic studies confirms that decomposition of the dyad occurs upon prolonged photolysis, and this appears to be a major factor for the low activity of the system toward H2 production in acidic conditions.

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Fast time-resolved IR studies of the excited states of co-ordination compound: direct observation of intramolecular charge transfer

Cited by 57 publications

References 0 publications

A Time-Resolved Infrared Vibrational Spectroscopic Study of the Photo-Dynamics of Crystalline Materials

A Time-Resolved Infrared Vibrational Spectroscopic Study of the Photo-Dynamics of Crystalline Materials

Ultrafast Excited State Dynamics Controlling Photochemical Isomerization of N‐Methyl‐4‐[trans‐2‐(4‐pyridyl)ethenyl]pyridinium Coordinated to a {Re^I(CO)₃(2,2′‐bipyridine)} Chromophore

Synthesis and Photophysical Study of a [NiFe] Hydrogenase Biomimetic Compound Covalently Linked to a Re-diimine Photosensitizer

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Fast time-resolved IR studies of the excited states of co-ordination compound: direct observation of intramolecular charge transfer

Cited by 57 publications

References 0 publications

A Time-Resolved Infrared Vibrational Spectroscopic Study of the Photo-Dynamics of Crystalline Materials

A Time-Resolved Infrared Vibrational Spectroscopic Study of the Photo-Dynamics of Crystalline Materials

Ultrafast Excited State Dynamics Controlling Photochemical Isomerization of N‐Methyl‐4‐[trans‐2‐(4‐pyridyl)ethenyl]pyridinium Coordinated to a {ReI(CO)3(2,2′‐bipyridine)} Chromophore

Synthesis and Photophysical Study of a [NiFe] Hydrogenase Biomimetic Compound Covalently Linked to a Re-diimine Photosensitizer

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Ultrafast Excited State Dynamics Controlling Photochemical Isomerization of N‐Methyl‐4‐[trans‐2‐(4‐pyridyl)ethenyl]pyridinium Coordinated to a {Re^I(CO)₃(2,2′‐bipyridine)} Chromophore