Photochemistry and Photophysics of Aromatic Sulfoxides. 1 Characterization of the Triplets at Cryogenic Temperatures

Jenks, William S.; Lee, Woo‐Jae; Shutters, D.

doi:10.1021/j100060a012

Cited by 58 publications

(66 citation statements)

References 13 publications

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“…Noteworthy, the emission lifetime of the upper energy band at 419 nm for 1 at 77 K is very long (3.4 ± 0.1 (85) and 0.38 ± 0.01 s (15%); fwhm = 1320 cm −1 ) and can only be associated with an intraligand phosphorescence, i.e., 3 ππ* in this case. Indeed, the phosphorescence bands of aryl thioethers are generally found between 382 and 433 nm with τ P detected in the 0.02-1.3 ms range in frozen solution at 77 K. [ 13 ] Conversely, the 3 XLCT/ 3 MLCT (T 2 →S 0 ) bands in cubane species appear in the vicinity of 440-450 nm, when observed, with τ P 's in the shorter μs time scale. [ 4c , 7a , 14 ] The Cu 8 I 8 cluster is a rather rare motif and to the best of our knowledge its chromophore properties have not been addressed.…”

Section: Absorption and Emission Spectroscopymentioning

confidence: 99%

Coordination RC₆H₄S(CH₂)₈SC₆H₄R/(CuI)_n Polymers (R (n) = H (4); Me (8)): An Innocent Methyl Group that Makes the Difference

Harvey

Bonnot

Lapprand

et al. 2015

Macromol. Rapid Commun.

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Under identical conditions, CuI reacts with PhS(CH2 )8 SPh and p-TolS(CH2 )8 STol-p affording, respectively, a luminescent 1D coordination polymer [Cu4 I4 {μ2 -PhS(CH2 )8 SPh}2 ]n (1) and an unprecedented 2D network [Cu8 I8 {μ2 -p-TolS(CH2 )8 STol-p}3 (MeCN)2 ]n (2), which incorporate closed-cubane Cu4 I4 and octanuclear Cu8 I8 clusters of as connecting nodes. Their thermal and photophysical properties exhibit notable differences.

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Section: Absorption and Emission Spectroscopymentioning

confidence: 99%

Coordination RC₆H₄S(CH₂)₈SC₆H₄R/(CuI)_n Polymers (R (n) = H (4); Me (8)): An Innocent Methyl Group that Makes the Difference

Harvey

Bonnot

Lapprand

et al. 2015

Macromol. Rapid Commun.

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“…[31][32][33] Also, it was well documented that aromatic sulfoxides are photochemically active molecules and characterisation of the triplet states of such simple organic molecules as PhEPh (E = S, SO, SO 2 ) has played a critical role in the development of their photochemistry and photophysics. [34,35] In the present work we report the first examples of Group 10-12 metal-acetylide polymers and their dinuclear congeners containing O, S, SO and SO 2 functionalities. These represent unprecedented model systems to evaluate how the chalcogen-based conjugation interrupters would limit the effective conjugation length of polymetallaynes.…”

Section: Introductionmentioning

confidence: 85%

Spatial Extent of the Singlet and Triplet Excitons in Luminescent Angular‐Shaped Transition‐Metal Diynes and Polyynes Comprising Non‐π‐Conjugated Group 16 Main Group Elements

Poon

Wong

Cheah

et al. 2006

Chemistry A European J

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A novel approach based on conjugation interruption has been developed and is presented for a series of luminescent and thermally stable chalcogen-bridged platinum(II) polyyne polymers trans-[{-Pt(PBu3)2C[triple bond]C(C6H4)E(C6H4)C[triple bond]C-}n] (E = O, S, SO, SO2). Particular attention was focused on the photophysical properties of these Group 10 polymetallaynes and comparison was made to their binuclear model complexes trans-[Pt(Ph)(PEt3)2C[triple bond]C(C6H4)E(C6H4)C[triple bond]CPt(Ph)(PEt3)2] and their closest Group 11 gold(I) and Group 12 mercury(II) neighbours, [MC[triple bond]C(C6H4)E(C6H4)C[triple bond]CM] (M = Au(PPh3), HgMe; E = O, S, SO, SO2). The regiochemical structures of these angular-shaped molecules were studied by NMR spectroscopy and single-crystal X-ray structural analyses. Upon photoexcitation, each one has an intense purple-blue fluorescence emission near 400 nm in dilute fluid solutions at room temperature. Harvesting of the organic triplet emissions harnessed through the strong heavy-atom effects of Group 10-12 transition metals was studied in detail. These metal-containing aryleneethynylenes spaced by chalcogen units were found to have large optical gaps and high-energy triplet states. The influence of metal- and chalcogen-based conjugation interrupters on the intersystem crossing rate and on the spatial extent of the lowest singlet and triplet excitons was fully elucidated. We discuss and compare the phosphorescence spectra of these transition-metal diynes and polyynes in terms of the nature of the metal centre, conjugated chain length and Group 16 spacer unit. Our work here indicates that high-energy triplet states in these materials intrinsically give rise to very efficient phosphorescence with fast radiative decays and one could readily observe room-temperature phosphorescence for the platinum polyynes.

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“…Jenks has shown that DBTO 19a is not photostable, 33 while DBTO 2 20a is, at least in solvents that are poor hydrogen donors. 34 Further photoirradiation leads to water soluble products, which one might expect to be biphenylsulfonates.…”

Section: Photooxygenation Of Dibenzothiophenes and Benzo[b]thiophenesmentioning

confidence: 99%

Photochemical and Electrochemical Oxygenation of Thiophenes, Benzo[b]Thiophenes and Dibenzothiophenes; Photochemical and Electrochemical Behaviour of Their Oxygenated Intermediates and Products

Thiemann

2010

Journal of Chemical Research

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Prof. Dr. Thies Thiemann received his chemical education at the universities of Hamburg and Tuebingen, Germany. After obtaining a PhD degree in organic chemistry at the University of Hamburg, he moved to Japan for his postdoctorate at Kyushu University, Fukuoka. Thies has also worked at joined the chemistry faculty of the United Arab Emirates University in Al Ain, Abu Dhabi. His main focus is on organic synthetic chemistry, especially in the areas of steroidal and heterocyclic chemistry. He is author/co-author of over 150 papers, nine reviews, three book chapters and five patents. S-oxides and benzo[b]thiopheneS,S-dioxides 672 6. Photochemistry of thiophene S-oxides 675 7. Electrochemical oxidation and reduction of thiophenes, thiophene S-oxides and related compounds 675 8. Conclusions 676 9. References 678The photooxygenation of thiophenes, benzo[b]thiophenes and dibenzothiophenes is discussed, especially in view of the oxidative removal of these S-containing contaminants from fuels. Furthermore, the photochemistry of the intermediates and the products from these processes is detailed. Finally, an account is given of the electrooxidation of thiophenes and derivatives to the corresponding sulfoxides and sulfones as well as of the electrochemical behaviour of the intermediate thiophene S-oxides.

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Photochemistry and Photophysics of Aromatic Sulfoxides. 1 Characterization of the Triplets at Cryogenic Temperatures

Cited by 58 publications

References 13 publications

Coordination RC₆H₄S(CH₂)₈SC₆H₄R/(CuI)_n Polymers (R (n) = H (4); Me (8)): An Innocent Methyl Group that Makes the Difference

Coordination RC₆H₄S(CH₂)₈SC₆H₄R/(CuI)_n Polymers (R (n) = H (4); Me (8)): An Innocent Methyl Group that Makes the Difference

Spatial Extent of the Singlet and Triplet Excitons in Luminescent Angular‐Shaped Transition‐Metal Diynes and Polyynes Comprising Non‐π‐Conjugated Group 16 Main Group Elements

Photochemical and Electrochemical Oxygenation of Thiophenes, Benzo[b]Thiophenes and Dibenzothiophenes; Photochemical and Electrochemical Behaviour of Their Oxygenated Intermediates and Products

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Photochemistry and Photophysics of Aromatic Sulfoxides. 1 Characterization of the Triplets at Cryogenic Temperatures

Cited by 58 publications

References 13 publications

Coordination RC6H4S(CH2)8SC6H4R/(CuI)n Polymers (R (n) = H (4); Me (8)): An Innocent Methyl Group that Makes the Difference

Coordination RC6H4S(CH2)8SC6H4R/(CuI)n Polymers (R (n) = H (4); Me (8)): An Innocent Methyl Group that Makes the Difference

Spatial Extent of the Singlet and Triplet Excitons in Luminescent Angular‐Shaped Transition‐Metal Diynes and Polyynes Comprising Non‐π‐Conjugated Group 16 Main Group Elements

Photochemical and Electrochemical Oxygenation of Thiophenes, Benzo[b]Thiophenes and Dibenzothiophenes; Photochemical and Electrochemical Behaviour of Their Oxygenated Intermediates and Products

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Coordination RC₆H₄S(CH₂)₈SC₆H₄R/(CuI)_n Polymers (R (n) = H (4); Me (8)): An Innocent Methyl Group that Makes the Difference

Coordination RC₆H₄S(CH₂)₈SC₆H₄R/(CuI)_n Polymers (R (n) = H (4); Me (8)): An Innocent Methyl Group that Makes the Difference