Enhancement of the Phosphorescence of Organic Luminophores upon Interaction with a Mercury Trifunctional Lewis Acid

Abstract

The interaction of the trinuclear mercury(II) complex [(o-C(6)F(4)Hg)(3)] (1) and pyrene leads to the formation of the 1:1 adduct 1.pyrene. The crystal structure of this adduct reveals the existence of supramolecular stacks in which molecules of 1 and molecules of pyrene alternate along the infinite chains. Steady-state and time-resolved photoluminescence measurements indicate the occurrence of a heavy atom effect which results in red, green, and blue (RGB) phosphorescent emissions for 1.pyrene, 1.naphthalene, and 1.biphenyl, respectively.

Phosphorescence sensitization via heavy-atom effects in d10 complexes

“…New adducts have been synthesized which contain an organic aromatic (arene) component and a heavy-metal inorganic component with an opposite p acid-base or donor-acceptor character [4][5][6][7][8][9]. The resulting adducts exhibit sensitized phosphorescence characteristic of the organic aromatic component owing to external HAE of the heavy-metal component in the vicinity of the arene.…”

“…For example, in collaboration with the Gabbaï group, we showed that bright RGB emissions characteristic of the triplet states of the electron-rich arenes are obtained upon their complexation with the electron-poor cyclic trimer Hg 3 (l-o-C 6 F 4 ) 3 (1), Fig. 1 [4]. In order to probe the extent of complexation between the arene and the mercury trimer, fluorescence spectroscopy was utilized (Fig.…”

“…The phosphorescence sensitization mechanism involves excitation to a charge-transfer (CT) state before intersystem crossing to the arene T 1 state (Fig. 3) [4][5][6][7].…”

Complexation of methylparathion and bis(2-hydroxyethyl)sulfide by the tridentate lewis acid [(o-C6F4Hg)3]

“…The trinuclear derivative 1 is one of the most studied examples of fluorinated polyfunctional organomercurials. It has been extensively employed for the complexation of anions and serves as a receptor for neutral organic substrates such as carbonyls [19][20][21][22], nitriles [23,24], sulfoxide [21], and aromatic substrates [25][26][27][28]. Recently, we also reported the formation of [1 · µ 6 -Me 2 S] n , a polymeric dimethyl sulfide adduct in which the sulfur is concomitantly coordinated to six mercury atoms provided by neighboring molecules of 1 [29].…”

Arene‐Sandwiched Silver(I) Pyrazolates

“…[15][16][17][18][19] The research group of Gabbaï has demonstrated its use in the isolation of a series of one-dimensional organometallic polymers (type A) which contain arene donors such as benzene, naphthalene, and pyrene. [20][21][22] During the synthesis of 1, [14] we observed that it was difficult to remove the aromatic solvent from the final product. A careful study of this behavior shows that 1 is indeed a good p acid and interacts with aromatic hydrocarbons through secondary Ag···p interactions to form interesting sandwich structures.…”