Spodium bonding to anticrown-Hg₃boosts phosphorescence of cyclometalated-Pt^IIcomplexes

Abstract

The moderately phosphorescent platinum(II) complexes [Pt(ppy)(acac)] (1; ppyH = 2-phenylpyridine, acacH = acetylacetone), [Pt(ppy)(hd)] (2; hdH = heptanedione-3,5), [Pt(ppy)(tmhd)] (3; tmhdH = 2,2,6,6-tetramethylheptanedione-3,5), [Pt(dfppy)(acac)] (4; dfppyH = 2-(2’,4’-difluorophenyl)pyridine), and [Pt(dfppy)(tmhd)]...

Hg(II)⋅d8[M] Interactions: Are they Metallophilic Interactions or Spodium Bonds?

“…In this manuscript, a different explanation for these Hg(II)⋅⋅⋅d 8 [M] (M=Pd, Pt) contacts detailed above is proposed, disclosing the electron acceptor role of the Hg(II) and the electron donor role of the d 8 [M] (M=Pd, Pt) counterpart. Therefore, these type of bonding can be considered as spodium bonding (SpB), as recently suggested by Kukushkin and coworkers in an interesting study where they demonstrated that spodium bonding boosts phosphorescence of cyclometalated‐Pt(II) complexes when interacting with an anticrown Hg 3 (1,2‐C 6 F 4 ) 3 compound [18] …”

“…Therefore, these type of bonding can be considered as spodium bonding (SpB), as recently suggested by Kukushkin and coworkers in an interesting study where they demonstrated that spodium bonding boosts phosphorescence of cyclometalated-Pt(II) complexes when interacting with an anticrown Hg 3 (1,2-C 6 F 4 ) 3 compound. [18]…”

Dichotomy of π-stacking-directing noncovalent forces in organic–inorganic planar assemblies: the case of halo-substituted benzoquinones π-stacked with a platinum(ii) square-plane

“…Other studies focused on organic-inorganic planar integrations considered noncovalent interactions with a nucleophilic d-orbital of a positively charged metal ion. [28][29][30][31][32][33][34][35][36][37][38][39][40] In particular, it has been demonstrated that square-planar platinum(II) complexes can act as integrated nucleophiles and function as π-hole acceptors via their filled d z 2[Pt II ] orbital and interact with π-hole donating electron-poor aromatics forming reverse sandwich systems. [29][30][31]33,34 In addition, we reported that electrondeficient aromatics easily sandwiched with the integrated d 8 [Pd]O 4 10 or d 8 [M]S 4 (M = Ni, Pd, Pt) 34 nucleophilic planes.…”

“…28–40 In particular, it has been demonstrated that square-planar platinum( ii ) complexes can act as integrated nucleophiles and function as π-hole acceptors via their filled d z 2 [Pt II ] orbital and interact with π-hole donating electron-poor aromatics forming reverse sandwich systems. 29–31,33,34 In addition, we reported that electron-deficient aromatics easily sandwiched with the integrated d 8 [Pd]O 4 10 or d 8 [M]S 4 (M = Ni, Pd, Pt) 34 nucleophilic planes. The metal sites donate their d z 2 -orbitals which, in combination with O or S lone pairs of the ligands, interact with the arene π-holes providing organic–inorganic pairing.…”

Incorporation of a Fluorine Atom in a Bridging Ligand of Half-Lantern PtII2 Complexes Provides up to 10-Fold Enhancement of Electroluminescence Brightness

“…In view of our interest in metal-involving halogen bond-based − supramolecular assembly of platinum­(II) complexes − and also in boosting the emission of platinum complexes by noncovalent interactions (e.g., by halogen bonding , or π–π interactions , ), we assumed that incorporation of a halogen atom in the bridging ligands should provide a key to improvement of luminescent properties of the half-lantern systems.…”