Solvent/solute interactions probed by picosecond transient Raman spectroscopy: mode-specific vibrational dynamics in S1 trans-stilbene

Weaver, W. R.; Huston, Lisa A.; Iwata, Koichi; Gustafson, Terry L.

doi:10.1021/j100201a047

Cited by 84 publications

(66 citation statements)

References 22 publications

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“…At early times, the peak maxima undergo a dynamic shift by about +5 cm À1 with lifetimes between 10-20 ps, due to vibrational cooling. [56,59,60] The band areas decay with kinetics commensurate with those of the TA bands.…”

Section: Photoisomerization: Irradiation Of Medpementioning

confidence: 87%

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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Section: Photoisomerization: Irradiation Of Medpementioning

confidence: 87%

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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“…[1][2][27][28][29][30][31] Studies reveal the dependence of electron transfer rates on a large number of parameters. 25,[32][33][34] Electron transfer rates have been observed to decrease with increasing nanocrystal size. 32 The constituent of the wide band gap semiconductor nanocrystal and shape of the constituents in the nano-heterostructure assembly have been observed to affect electron transfer processes.…”

Section: Introductionmentioning

confidence: 98%

Probing Ultrafast Photoinduced Electron Transfer to TiO₂ from CdS Nanocrystals of Varying Crystallographic Phase Content

Mazumdar¹,

Roy²,

Srihari

et al. 2015

J. Phys. Chem. C

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The photoinduced electron transfer processes in a nano-heterostructured semiconductor assembly are complex and depend on various parameters of the constituents of the assembly. We present here the ultrafast electron transfer characteristics of an assembly comprising of a wide band semiconductor, titanium dioxide (TiO 2 ) attached to light harvesting cadmium sulfide (CdS) nanocrystals of varying crystallographic phase content. Quantitative analysis of synchrotron high resolution X-ray diffraction data of CdS nanocrystals precisely reveal the presence of both wurtzite and zinc blende phases in varying amounts. The estimated content of crystal phases is observed to be strongly dependent on an important synthesis parameter viz. the ratio of the two solvents. The biphasic nature of CdS influences directly the shape of the nanocrystal at long reaction times as well as the transfer of the photo-excited electrons from the CdS to TiO 2 as obtained from transient absorption spectroscopy. Higher amount of zinc blende phase is observed to be beneficial for fast electron transfer across the CdS-TiO 2 interface. The electron transfer rate constant differs by one order in magnitude between the CdS nanocrystals and varies linearly with the fraction of the phases.

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“…Indeed, two groups have recently reported picosecond R R studies of S1 trans-stilbene in a l k a n e~~~, * 3 and acetonitrile. 21 We report on VC studies of trans-stilbene in both alkanes and alcohols employing a R R spectrometer with better time resolution than those employed in the two previous studies.…”

Section: Introductionmentioning

confidence: 98%

Picosecond resonance Raman studies of vibrational cooling of electronically excited trans-stilbene in alcohols and alkanes

Qian¹,

Schultz²,

Bradburn³

et al. 1993

J. Phys. Chem.

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The vibrational cooling of electronically excited trans-stilbene has been studied in ethanol, hexanol, hexane, and decane by pump-probe resonance Raman ( R R ) spectroscopy employing pulses of 1.5-2.0 ps with 15 cm-I spectral width. Excitation 3200 cm-' above the electronic origin creates a transient rise in the stilbene vibrational temperature of approximately 150 K. The subsequent intermolecular transfer of this excess energy to the surrounding solvent leads to time-dependent changes in the peak position and bandwidth of the ethyleneic band a t -1565 cm-1. In agreement with previous studies, we find that the lineshape of this mode is nearly Lorentzian a t all delay times and that the width decays exponentially with increasing delay time. The peak position, however, shifts to higher frequency only after a 3-5-ps induction period. The vibrational cooling kinetics, as measured by the dynamics of the bandwidth, d o not depend on solvent, though the dephasing time of the ethylenic mode is faster in alcohols than in alkanes. We interpret these results as arising from coupling of the ethylenic motion to two or more low frequency modes that can exchange energy with the solvent via collisions.W e discuss the role of solvent-solute interactions and solvent thermal conduction in the cooling process.

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Solvent/solute interactions probed by picosecond transient Raman spectroscopy: mode-specific vibrational dynamics in S1 trans-stilbene

Cited by 84 publications

References 22 publications

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

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

Probing Ultrafast Photoinduced Electron Transfer to TiO₂ from CdS Nanocrystals of Varying Crystallographic Phase Content

Picosecond resonance Raman studies of vibrational cooling of electronically excited trans-stilbene in alcohols and alkanes

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Solvent/solute interactions probed by picosecond transient Raman spectroscopy: mode-specific vibrational dynamics in S1 trans-stilbene

Cited by 84 publications

References 22 publications

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

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

Probing Ultrafast Photoinduced Electron Transfer to TiO2 from CdS Nanocrystals of Varying Crystallographic Phase Content

Picosecond resonance Raman studies of vibrational cooling of electronically excited trans-stilbene in alcohols and alkanes

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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

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

Probing Ultrafast Photoinduced Electron Transfer to TiO₂ from CdS Nanocrystals of Varying Crystallographic Phase Content