Photoinduced Ullmann C-N coupling: demonstrating the viability of a radical pathway.

Carbon-nitrogen (C-N) bond-forming reactions of amines with aryl halides to generate arylamines (anilines), mediated by a stoichiometric copper reagent at elevated temperature (>180°C), were first described by Ullmann in 1903. In the intervening century, this and related C-N bond-forming processes have emerged as powerful tools for organic synthesis. Here, we report that Ullmann C-N coupling can be photoinduced by using a stoichiometric or a catalytic amount of copper, which enables the reaction to proceed under unusually mild conditions (room temperature or even -40°C).

Efficient luminescence from easily prepared three-coordinate copper(I) arylamidophosphines.

A series of brightly luminescent, three-coordinate copper(I) arylamidophosphine complexes have been prepared from readily available precursors in high yield. Emission maxima span 102 nm in the visible spectrum from 461 (blue) to 563 nm (yellow) while photoluminescence quantum yields range from 0.11 to 0.

Platinum(II) terpyridyl-acetylide dyads and triads with nitrophenyl acceptors via a convenient synthesis of a boronated phenylterpyridine.

Four new Pt(II) terpyridyl acetylide complexes which possess a covalently linked nitrophenyl moiety were prepared and studied. Specifically, the chromophore-acceptor (C-A) dyads reported here include [Pt(ptpy-ph-p-NO(2))(C[triple bond]C-C(6)H(5))](PF(6))(3) (1), where ptpy-ph-p-NO(2) = 4'-{4-(4-nitrophenyl)-phenyl}-[2,2';6',2'']terpyridine, and C[triple bond]C-C(6)H(5) = phenylacetylide and [Pt(ptpy-ph-m-NO(2))(C[triple bond]C-C(6)H(5))](PF(6))(2) (2), where ptpy-ph-m-NO(2) = 4'-(4-m-nitrophenyl-phenyl)-2,2';6',2''-terpyridine, as well as the related donor-chromophore-acceptor (D-C-A) triads [Pt(ptpy-ph-p-NO(2))(C[triple bond]C-C(6)H(4)CH(2)-PTZ)]PF(6) (3), where C[triple bond]C-C(6)H(4)CH(2)-PTZ = 4-ethynylbenzyl-N-phenothiazine, and [Pt(ptpy-ph-m-NO(2))(C[triple bond]C-C(6)H(4)CH(2)-PTZ)]PF(6) (4). Transient absorption spectroscopy and electrochemical analyses were used to characterize these compounds.