Transient DC Photocurrent Investigation of Charge Redistribution within Re(CO)<sub>3</sub>Cl(2,2‘-bipyridine): An Unexpected Decrease in Molecular Dipole Moment upon Emissive Excited-State Formation

Vanhelmont, Frederik W. M.; Hupp, Joseph T.

doi:10.1021/ic991285n

Cited by 19 publications

(19 citation statements)

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“…9 A possible explanation for these shifts arises from a study by Vanhelmont and Hupp that includes a calculation of the spatial orientation of the ground and excited state dipoles in fac-Re(bpy)(CO) 3 Cl. 28 This study indicates that the ground state dipole is approximately aligned with the Re-Cl bond while the excited state dipole is aligned nearly to the local C 3 axis formed by the carbonyl groups. Based on this, the excited state dipole should be pointing to the ZrP plane, where it can be stabilized by interaction with the phosphate groups, producing red shifts.…”

Section: Resultsmentioning

confidence: 72%

Intercalation of Re(phen)(CO)₃Cl into zirconium phosphate: a water insoluble inorganic complex immobilized in a highly polar rigid matrix

et al. 2007

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The intercalation of fac-tricarbonylchloro-1,10-phenanthrolinerhenium(i) (Re(phen)(CO)(3)Cl) within zirconium phosphate (ZrP) has been achieved using a hydrated ZrP phase that possesses six water molecules per formula unit. This intercalation occurs only at high solution molar ratios (Re : ZrP, 3 : 1) and is characterized by the emergence of a new phase in the X-ray powder diffraction (XRPD) pattern with an interlayer distance of 15.6 A. The XRPD patterns show a decrease in the crystallinity upon intercalation of the inorganic complex. The MLCT absorption bands of Re(phen)(CO)(3)Cl-containing ZrP materials are red shifted in comparison with the complex in acetonitrile whilst the luminescence spectra at different loading levels are blue shifted up to 30 nm in comparison with the complex in acetonitrile. This blue shift is consistent with the rigidochromic effect. The luminescence lifetime of Re(phen)(CO)(3)Cl within ZrP was increased in comparison with its lifetime in acetonitrile solution but is shorter than that of Re(phen)(CO)(3)Cl in frozen glass and polyesther resins. To our knowledge, this is the first example of a water insoluble metal complex intercalated within the layers of ZrP, which opens up new possibilities in the intercalation chemistry of this lamellar material and in the study of host-guest interactions.

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Section: Resultsmentioning

confidence: 72%

Intercalation of Re(phen)(CO)₃Cl into zirconium phosphate: a water insoluble inorganic complex immobilized in a highly polar rigid matrix

et al. 2007

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“…Optical excitation of the metal-to-ligandcharge-transfer (MLCT) band at 400 nm promotes an electron from a Re d orbital to the π* orbital of the bipyridine, from which electron transfer into ATO occurs. 29,32,[48][49][50][51][52][53][54][55][56][57][58][59][60] Transient IR difference spectra of ReC1PO 3 on 10% ATO in the higher frequency CO stretching mode region are shown in Figure 4. These spectra are averaged over about 10 delay times in the selected time delay windows: 0.5-1, 2-10, 15-50, 150-350 and 400-800 ps.…”

Section: Resultsmentioning

confidence: 99%

“…Hereafter, we will focus our discussion on the higher frequency mode to avoid the complexity of such spectral overlap. Optical excitation of the metal-to-ligand-charge-transfer (MLCT) band at 400 nm promotes an electron from a Re d orbital to the π* orbital of the bipyridine, from which electron transfer into ATO occurs. ,,− …”

Section: Resultsmentioning

confidence: 99%

Ultrafast Electron Transfer between Molecule Adsorbate and Antimony Doped Tin Oxide (ATO) Nanoparticles

2005

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Ultrafast transient IR spectroscopy has been used to examine the effect of doping on interfacial electron transfer (ET) dynamics in Re(dpbpy)(CO)(3)Cl (dpbpy = 4,4'-(CH(2)PO(OH)(2))2-2,2'-bipyridine) (ReC1PO(3)) sensitized ATO (Sb:SnO(2)) nanocrystalline thin films. In films consisting of particles with 0%, 2% and 10% Sb dopant, the rates of electron injection from the adsorbate excited state to ATO were independent of and the rates of the recombination increased with the doping level. The observed similar forward electron injection rates were attributed to negligible changes of available accepting states in the conduction band at the doping levels studied. The dependence of the recombination rate on conduction band electron density and a possible mechanism for the recombination process were discussed.

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“…Rhenium diimine complexes of the type fac-[Re I (LL)-(CO) 3 L′] n+ (n ) 0, 1; LL ) diimine ligand) have been well studied because they are excellent emitters, 1,8-10 photocatalysts, 6,[11][12][13][14][15][16] and building blocks for supramolecules. 5,[17][18][19] Although a tremendous number of fundamental studies of the photophysics of these rhenium complexes have been carried out over the last two decades, the targets of these studies have been only triplet CT excited statesssuch as metal-to-ligand ( 3 MLCT), 8,[20][21][22][23][24][25] ligand-to-ligand ( 3 LLCT), 18,26 and σ-to-ligand ( 3 σ-π*) 2,27-29 statessand 3 LC excited states. [30][31][32] In contrast, little is known about the LF states of these rhenium diimine complexes.…”

Section: Introductionmentioning

confidence: 99%

Mechanism of the Photochemical Ligand Substitution Reactions of fac-[Re(bpy)(CO)₃(PR₃)]⁺ Complexes and the Properties of Their Triplet Ligand-Field Excited States

et al. 2002

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We report herein the mechanism of the photochemical ligand substitution reactions of a series of fac-[Re(X(2)bpy)(CO)(3)(PR(3))](+) complexes (1) and the properties of their triplet ligand-field ((3)LF) excited states. The reason for the photostability of the rhenium complexes [Re(X(2)bpy)(CO)(3)(py)](+) (3) and [Re(X(2)bpy)(CO)(3)Cl] (4) was also investigated. Irradiation of an acetonitrile solution of 1 selectively gave the biscarbonyl complexes cis,trans-[Re(X(2)bpy)(CO)(2)(PR(3))(CH(3)CN)](+) (2). Isotope experiments clearly showed that the CO ligand trans to the PR(3) ligand was selectively substituted. The photochemical reactions proceeded via a dissociative mechanism from the (3)LF excited state. The thermodynamical data for the (3)LF excited states of complexes 1 and the corrective nonradiative decay rate constants for the triplet metal-to-ligand charge-transfer ((3)MLCT) states were obtained from temperature-dependence data for the emission lifetimes and for the quantum yields of the photochemical reactions and the emission. Comparison of 1 with [Re(X(2)bpy)(CO)(3)(py)](+) (3) and [Re(X(2)bpy)(CO)(3)Cl] (4) indicated that the (3)LF states of some 3- and 4-type complexes are probably accessible from the (3)MLCT state even at ambient temperature, but these complexes were stable to irradiation at 365 nm. The photostability of 3 and 4, in contrast to 1, can be explained by differences in the trans effects of the PR(3), py, and Cl(-) ligands.

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Transient DC Photocurrent Investigation of Charge Redistribution within Re(CO)₃Cl(2,2‘-bipyridine): An Unexpected Decrease in Molecular Dipole Moment upon Emissive Excited-State Formation

Cited by 19 publications

References 32 publications

Intercalation of Re(phen)(CO)₃Cl into zirconium phosphate: a water insoluble inorganic complex immobilized in a highly polar rigid matrix

Intercalation of Re(phen)(CO)₃Cl into zirconium phosphate: a water insoluble inorganic complex immobilized in a highly polar rigid matrix

Ultrafast Electron Transfer between Molecule Adsorbate and Antimony Doped Tin Oxide (ATO) Nanoparticles

Mechanism of the Photochemical Ligand Substitution Reactions of fac-[Re(bpy)(CO)₃(PR₃)]⁺ Complexes and the Properties of Their Triplet Ligand-Field Excited States

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Transient DC Photocurrent Investigation of Charge Redistribution within Re(CO)3Cl(2,2‘-bipyridine): An Unexpected Decrease in Molecular Dipole Moment upon Emissive Excited-State Formation

Cited by 19 publications

References 32 publications

Intercalation of Re(phen)(CO)3Cl into zirconium phosphate: a water insoluble inorganic complex immobilized in a highly polar rigid matrix

Intercalation of Re(phen)(CO)3Cl into zirconium phosphate: a water insoluble inorganic complex immobilized in a highly polar rigid matrix

Ultrafast Electron Transfer between Molecule Adsorbate and Antimony Doped Tin Oxide (ATO) Nanoparticles

Mechanism of the Photochemical Ligand Substitution Reactions of fac-[Re(bpy)(CO)3(PR3)]+ Complexes and the Properties of Their Triplet Ligand-Field Excited States

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Transient DC Photocurrent Investigation of Charge Redistribution within Re(CO)₃Cl(2,2‘-bipyridine): An Unexpected Decrease in Molecular Dipole Moment upon Emissive Excited-State Formation

Intercalation of Re(phen)(CO)₃Cl into zirconium phosphate: a water insoluble inorganic complex immobilized in a highly polar rigid matrix

Intercalation of Re(phen)(CO)₃Cl into zirconium phosphate: a water insoluble inorganic complex immobilized in a highly polar rigid matrix

Mechanism of the Photochemical Ligand Substitution Reactions of fac-[Re(bpy)(CO)₃(PR₃)]⁺ Complexes and the Properties of Their Triplet Ligand-Field Excited States