The half-lantern PtII2 complexes [Pt(CN)(μ-SN)]2 (HCN = 2-phenylbenzothiazolate 1; 2-naphtylbenzothiazolate 2; HSN = 2-thiopyridine) were crystallized with such electron-deficient arenes as hexafluorobenzene (C6F6) and octafluoroanthraquinone (OFA) to give cocrystals 1·C6F6,...

Perfluorinated arenes (perfluoropyridine, perfluorotoluene, and perfluorobiphenyl) were converted to the bis-(perfluoroaryl)chalcolanes Ar F 2 Ch (Ch = S 59−88%, Se 54−84%, Te 10−41%) via the developed one-pot methodology. This method includes the generation of Na 2 Ch (formed in situ by the reduction of Ch with the system Na + [C 10 H 8 ] •− ) followed by its treatment with any one of the arenes. The crystal structures of (4-NC 5 F 4 ) 2 S (2), (C 12 F 9 ) 2 S (3) (p-CF 3 C 6 F 4 ) 2 Se (4), (C 12 F 9 ) 2 Se (6 A,B ; two polymorphs), (C 12 F 9 ) 2 Te (9), and (4-NC 5 F 4 ) 2 Te (8 B ; a novel polymorph) were determined by X-ray crystallography. In the solid state, compounds Ar F 2 Ch are self-associated via σ-(Ch)hole interactions with F (or N for 8 B ) and also π−π stacking between the arenes. The σ/π-hole donor properties of Ar F 2 Ch were evaluated by molecular electrostatic potential surface analysis using the density functional theory approach. The maximum V s (σ-hole) values (from +25 to +38 kcal/mol) increase in the order S < Se < Te along with an increase in the polarizability and decrease in the electronegativity of the Ch sites, while the π-hole depths (+14 to +20 kcal/mol) follow the opposite trend being the lowest for the Te II derivatives.

The binuclear half-lantern platinum(II) complexes [Pt-(pbt)(μ-S ∧ N)] 2 (pbtH = 2-phenylbenzothiazole, S ∧ N = benzo[d]thiazole-2-thiolate Pt1, 6-fluorobenzo[d]thiazole-2-thiolate Pt2, 6-chlorobenzo[d]thiazole-2-thiolate Pt3, 6-bromobenzo[d]thiazole-2-thiolate Pt4, and 6iodobenzo[d]thiazole-2-thiolate Pt5) were synthesized by the treatment of the in situ formed [Pt(pbt)(NCMe) 2 ]NO 3 complex and appropriate benzo[d]thiazole-2-thiole in the presence of t BuOK; yield: 51−84%. Complexes Pt1-5 exhibit intense red photoluminescence originated from 3MMLCT state reaching 22% room temperature quantum yields in a CH 2 Cl 2 solution. All complexes display excited-state decay kinetics both in solution and in the solid state; the kinetics was adequately modeled by single exponentials. The complexes display more than 10-fold higher electroluminescence brightness for the F-containing Pt2 (900 cd/m 2 ) and 2-fold higher electroluminescence brightness for the Cl-containing Pt3 (143 cd/m 2 ) compared to the H-substituted complex Pt1 (77 cd/m 2 ). It is argued that this impressive device luminance growth, occurred on formal replacement of H-to-F, is associated with the intermolecular strong hydrogen bonding H•••F relevant to the H-bond found in the structure of Pt2.

No abstract