Synthesis, Characterization, and Photophysics of a New Trinuclear Mercury(II) Complex of 1,3,5-Triethynylbenzene

2006 ◽  
Vol 59 (7) ◽  
pp. 434 ◽  
Author(s):  
Li Liu ◽  
Wai-Yeung Wong ◽  
Cheuk-Lam Ho
Keyword(s):  
Excited State ◽  
Photophysical Properties ◽  
Heavy Atom ◽  
High Energy ◽  
Intersystem Crossing ◽  
Spectroscopic Techniques ◽  
Triplet States ◽  
Ambient Conditions ◽  
Triplet Excited States ◽  
Atom Effect

A new trinuclear mercury(ii) complex of 1,3,5-triethynylbenzene [(MeHgC≡C)3(1,3,5-C6H3)] 1 was prepared in good yield by Hagihara’s dehydrohalogenation reaction of HgMeCl with [(HC≡C)3(1,3,5-C6H3)] under ambient conditions. This trimercury triacetylide complex’s structure was confirmed by common spectroscopic techniques and its photophysical properties were examined and compared with the isolobal gold(i) congener [{(PPh3)AuC≡C}3(1,3,5-C6H3)] 2. Our investigations indicate that the organic triplet emissions can be harvested by the heavy-atom effect of mercury which enables efficient intersystem crossing from the S1 singlet excited state to the T1 triplet excited state. The influence of Hg and Au centres on the phosphorescence efficiency and evolution of the lowest electronic singlet and triplet excited states is critically characterized. Both complexes 1 and 2 possess high-energy triplet states of 2.77–2.82 eV, in which the order of intersystem crossing rate follows the order Au > Hg.

Competition between the heavy atom effect and vibronic coupling in donor–bridge–acceptor organometallics

2020 ◽  
Vol 22 (8) ◽  
pp. 4659-4667 ◽  
Author(s):  
Julien Eng ◽  
Stuart Thompson ◽  
Heather Goodwin ◽  
Dan Credgington ◽  
Thomas James Penfold
Keyword(s):  
Excited State ◽  
Quantum Dynamics ◽  
Heavy Atom ◽  
Vibronic Coupling ◽  
Intersystem Crossing ◽  
Heavy Atom Effect ◽  
Metal Amides ◽  
Coinage Metals ◽  
Dynamics Simulations ◽  
Atom Effect

The excited state properties and intersystem crossing dynamics of a series of donor–bridge–acceptor carbene metal-amides based upon the coinage metals Cu, Ag, Au, are investigated using quantum dynamics simulations and supported by photophysical characterisation.

scholarly journals Fluorescence properties of halogenated mono-hydroxyl corroles: the heavy-atom effects

2009 ◽  
Vol 13 (12) ◽  
pp. 1221-1226 ◽  
Author(s):  
Lei Shi ◽  
Hai-Yang Liu ◽  
Han Shen ◽  
Jun Hu ◽  
Guo-Liang Zhang ◽  
...  
Keyword(s):  
Fluorescence Spectra ◽  
Halogen Atom ◽  
Photophysical Properties ◽  
Heavy Atom ◽  
Phenyl Group ◽  
Atomic Weight ◽  
Quantum Yields ◽  
Intersystem Crossing ◽  
Fluorescence Quantum Yields ◽  
Atom Effect

A series of mono-hydroxyl corrole bearing a fluorine (1), chlorine (2), bromine (3) and iodine (4) atom on its 10-phenyl group have been synthesized. Fluorescence spectroscopy shows that the halogen atom at meso-phenyl group of corroles exhibit significant heavy-atom effect on their photophysical properties. Fluorescence quantum yields and the lifetime of these corroles decrease with the increasing of the atomic weight of halogen atoms. The quenching of the fluorescence could be interpreted in terms of a heavy atom-induced increase in intersystem crossing from S1 to T1. The intersystem crossing rate constant of these corroles were also determined by transient fluorescence spectra.

scholarly journals Unexpectedly Long Lifetime of the Excited State of Benzothiadiazole Derivative and Its Adducts with Lewis Acids

Molecules ◽  
2021 ◽  
Vol 26 (7) ◽  
pp. 2030
Author(s):  
Taisiya S. Sukhikh ◽  
Radmir M. Khisamov ◽  
Sergey N. Konchenko
Keyword(s):  
Lewis Acids ◽  
Bromine Atom ◽  
Heavy Atom ◽  
Intersystem Crossing ◽  
Triplet States ◽  
X Ray Diffraction ◽  
X Ray ◽  
Singlet And Triplet States ◽  
Long Lifetime ◽  
Atom Effect

We report a study of photoluminescent properties of 4-bromo-7-(3-pyridylamino)-2,1,3-benzothiadiazole (Py-btd) and its novel Lewis adducts: (PyH-btd)2(ZnCl4) and [Cu2Cl2(Py-btd)2{PPO}2]·2C7H8 (PPO = tetraphenyldiphosphine monoxide), whose crystal structure was determined by X-ray diffraction analysis. Py-btd exhibits a lifetime of 9 microseconds indicating its phosphorescent nature, which is rare for purely organic compounds. This phenomenon arises from the heavy atom effect: the presence of a bromine atom in Py-btd promotes mixing of the singlet and triplet states to allow efficient singlet-to-triplet intersystem crossing. The Lewis adducts also feature a microsecond lifetime while emitting in a higher energy range than free Py-btd, which opens up the possibility to color-tune luminescence of benzothiadiazole derivatives.

Enhancement of Reverse Intersystem Crossing in Charge‐Transfer Molecule through Internal Heavy Atom Effect

2021 ◽  
pp. 2104646
Author(s):  
Hyung Suk Kim ◽  
Ja Yeon Lee ◽  
Seongjun Shin ◽  
Wonkyo Jeong ◽  
Sang Hoon Lee ◽  
...  
Keyword(s):  
Charge Transfer ◽  
Heavy Atom ◽  
Intersystem Crossing ◽  
Heavy Atom Effect ◽  
Atom Effect

Löschung der Perylen-Fluoreszenz durch Ag+ -Ionen / Quenching of the Perylene Fluorescence by Ag+-Ions

1983 ◽  
Vol 38 (6) ◽  
pp. 698-700 ◽  
Author(s):  
H. Dreeskamp ◽  
A. Läufer ◽  
M. Zander
Keyword(s):  
Triplet State ◽  
Dynamic Process ◽  
Aromatic Compounds ◽  
Heavy Atom ◽  
Silver Ions ◽  
Intersystem Crossing ◽  
Fluid Solution ◽  
Long Wavelength ◽  
Wavelength Emission ◽  
Atom Effect

The fluorescence of perylene in fluid solution (λ0.0 = 440 nm) is quenched by silver ions in a dynamic process according to a Stern-Volmer kinetics (kq = 2 · 109 [1 • mol-1 · sec-1], in ethanol at 295 K). Simultaneously an unstructured long-wavelength emission (λmax ≈ 470 nm) appears which we assign to a perylene/Ag+ exciplex. A similar emission is observed when other polvcyclic aromatic compounds (PAC) are used, whose fluorescence as in the case of perylene is not easily quenched in an external heavy atom effect by iodopropane (kq ≦ 106). In these cases the excited PAC/Ag+ complex is long-lived enough to emit fluorescence since the intersystem crossing to the triplet system is slow due to the absence of an energetically favorable accepting triplet state

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