Photoemission from tungsten alkylidyne complexes in fluid solution

Bocarsly, Andrew Bruce; Cameron, R. E.; Rubin, H.-D.; McDermott, Gregory A.; Wolff, C. R.; Mayr, Andreas

doi:10.1021/ic00218a002

Cited by 50 publications

(45 citation statements)

References 3 publications

(4 reference statements)

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“…However, the difference spectrum with and without the laser pump pulse clearly displays oscillatory features that support the evidence for the bond lengthening in the excited state (Lovaasen et al, 2010). The tungsten-alkylidyne (or carbyne) with formal d 2 octahedral structure can bind ligands with diverse electronic structures, including strong acids and donors and hard and soft bases (Bocarsly et al, 1985(Bocarsly et al, , 1987Carter et al, 1991;Pollagi et al, 1994;Trammell et al, 1995;Schoch et al, 1996;Xue et al, 1996Xue et al, , 1997Xue et al, , 1998Lee et al, 1998;Cavalheiro et al, 1999;Mayr et al, 1999;Lai et al, 2001;Simpson et al, 2003;Jelliss & Wampler, 2005), which tunes the photophysical and photoredox properties or even changes the orbital character of the emissive state among d ! *, !…”

Section: Mlct States Of the Second-and Third-row Transition Metal Commentioning

confidence: 99%

Excited-state molecular structures captured by X-ray transient absorption spectroscopy: a decade and beyond

Chen

Zhang

Lockard

et al. 2010

Acta Crystallogr A Found Crystallogr

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Transient molecular structures along chemical reaction pathways are important for predicting molecular reactivity, understanding reaction mechanisms, as well as controlling reaction pathways. During the past decade, X-ray transient absorption spectroscopy (XTA, or LITR-XAS, laser-initiated X-ray absorption spectroscopy), analogous to the commonly used optical transient absorption spectroscopy, has been developed. XTA uses a laser pulse to trigger a fundamental chemical process, and an X-ray pulse(s) to probe transient structures as a function of the time delay between the pump and probe pulses. Using X-ray pulses with high photon flux from synchrotron sources, transient electronic and molecular structures of metal complexes have been studied in disordered media from homogeneous solutions to heterogeneous solution-solid interfaces. Several examples from the studies at the Advanced Photon Source in Argonne National Laboratory are summarized, including excited-state metalloporphyrins, metal-to-ligand charge transfer (MLCT) states of transition metal complexes, and charge transfer states of metal complexes at the interface with semiconductor nanoparticles. Recent developments of the method are briefly described followed by a future prospective of XTA. It is envisioned that concurrent developments in X-ray free-electron lasers and synchrotron X-ray facilities as well as other table-top laser-driven femtosecond X-ray sources will make many breakthroughs and realise dreams of visualizing molecular movies and snapshots, which ultimately enable chemical reaction pathways to be controlled.

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Section: Mlct States Of the Second-and Third-row Transition Metal Commentioning

confidence: 99%

Excited-state molecular structures captured by X-ray transient absorption spectroscopy: a decade and beyond

Chen

Zhang

Lockard

et al. 2010

Acta Crystallogr A Found Crystallogr

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“…Fast atom bombardment (FAB) mass spectra were obtained on a Finnigan Mat 95 mass spectrometer. 1 H (300 MHz) and 13 C (126 MHz) spectra were recorded on DPX 300 and 500 Bruker FT-NMR spectrometers, respectively, with chemical shift (in ppm) relative to tetramethylsilane. Elemental analysis was performed by the Institute of Chemistry at the Chinese Academy of Sciences, Beijing.…”

Section: General Proceduresmentioning

confidence: 99%

“…Our endeavors in developing luminescent metal-carbon multiple-bonded species have also proved fruitful for low-valent Pt(II) [8] and Re(I) [9] carbene derivatives supported by diimine auxiliaries, while the preparation and excited-state properties of high-valent Re(V) [10,11] and -(VI) [12] alkylidyne luminophores have been undertaken; an overview of this body of work is given at the end of this account. Mayr et al [13] first noted fluid luminescence from alkylidyne complexes in 1985, but reports of further examples remain sparse [14,15].…”

Section: Introductionmentioning

confidence: 99%

Luminescent metal complexes derived from carbene and related ligands: tuning excited-state properties with metal–carbon multiple bonds

Lai

Chan

Wang

et al. 2001

Journal of Organometallic Chemistry

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“…The phenylcarbyne complexes Va-Vd give similar spectra with two main features: a strong band in the 320-330-nm range (molar absorptivity e = 5x 10 3 -1 χ 10 4 ) and a much weaker absorption in the 480-500-nm range (€ = 50-200). These transi tions were assigned by analogy to the spectra of X(CO) 2 L 2 W=CR [R is Ph or r-Bu; X is CI or Br; L 2 = tetramethylethylenediamine (tmeda), dipyridine (py^, or l,2-bis(diphenylphosphino)ethane (dppe)] described by Boearsly and co-workers (30,31). The 320-nm peaks are taken to arise from intraligand transitions in the phenyl substituents of arylcarbyne ligands.…”

Section: Electronic Structure and Spectroscopy Of Metal Carbynesmentioning

confidence: 99%

Photooxidation of Metal Carbynes

McElwee‐White

Kingsbury

Carter

1993

Photosensitive Metal—Organic Systems

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Radical cations formed upon photooxidation of the metal carbyne complexes (n 5 -C 5 H 5 )L 1 L 2 M≡CR (M is Mo or W; L 1 and L 2 are CO or P(OMe) 3 ; and R is alkyl or aryl) were found to be extremely reactive. Depending on the reaction conditions, either the radical cations exhibited the ligand-exchange and atom--abstraction processes that are typical of metal radicals, or the carbyne ligands underwent a series of highly unusual rearrangements to yield organic products. When organic products were generated, they were formed with good stereochemical and regiochemical control.REACTIVE ORGANIC FRAGMENTS CAN BE STABILIZED with transi tion metals so that they can be used for synthesis under ordinary reaction conditions. One example is the extensive utilization of metal carbenes in organic synthesis (2). It is thus somewhat surprising that there are so few reported cases of generation of organic products from the closely related metal carbynes. Although the chemistry of metal carbynes has been explored (2), most of the reported reactions involve conversion into other carbyne complexes by exchange of ancillary ligands; interconversion of car byne, carbene, and vinylidene complexes; or [2 + 2] cycloaddition with alkenes and alkynes followed by metathesis or polymerization. With the exception of polymers and metathesis products, organic species derived from the carbyne ligand are almost never generated.One method for inducing new modes of reactivity in metal complexes is one-electron (l-e~) oxidation. The differences in reaction rates between 18-e~ complexes and their 17-e~ counterparts can be quite dramatic (3-5). Reaction manifolds that are not available to an 18-e~ complex can thus become accessible to its corresponding 17-e~ radical cation. This chapter

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Photoemission from tungsten alkylidyne complexes in fluid solution

Cited by 50 publications

References 3 publications

Excited-state molecular structures captured by X-ray transient absorption spectroscopy: a decade and beyond

Excited-state molecular structures captured by X-ray transient absorption spectroscopy: a decade and beyond

Luminescent metal complexes derived from carbene and related ligands: tuning excited-state properties with metal–carbon multiple bonds

Photooxidation of Metal Carbynes

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