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SP 1 sp H NMR (300 MHz, acetone- I d i SB 6 sb ): = 11.66 (s, 1 H, H SB N-H sb ), 8.39 (d, I J i = 8.2 Hz, 1 H, H SB 7 sb ), 8.35 (d, I J i = 2.6 Hz, 1 H, H SB 2 sb ), 8.12 (d, I J i = 8.3 Hz, 1 H, H SB 6 sb ). SP 1 sp H NMR (300 MHz, acetone- I d i SB 6 sb ): = 11.49 (s, 1 H, H SB N-H sb ), 8.78 (d, I J i = 2.3 Hz, 1 H, H SB 5 sb ), 8.46 (d, I J i = 2.3 Hz, 1 H, H SB 7 sb ), 8.30 (d, I J i = 2.8 Hz, 1 H, H SB 2 sb ), 8.17-8.07 (m, 2 H, H SB 10or11 sb ), 8.03-7.94 (m, 2 H, H SB 10or11 sb ). SP 13 sp C NMR (75 MHz, acetone- I d i SB 6 sb ): = 157.11 (d, I J i = 15.3 Hz, C SB 4 sb ), 155.38 (dd, I J i = 263.6, 4.4 Hz, Cq), 150.58 (dd, I J i = 253.0, 4.6 Hz, Cq), 148.32 (Cq), 147.54 (C SB 2 sb ), 121.72 (Cq), 120.75 (d, I J i = 3.6 Hz, Cq), 120.03 (Cq), 120.0-104.00 (m, C SB CF sb ). SP 13 sp C NMR (75 MHz, acetone- I d i SB 6 sb ): = 159.44 (C SB 4 sb ), 155.77 (dd, I J i = 266.4, 19.7 Hz, Cq), 150.08 (dd, I J i = 250.8, 15.1 Hz, Cq), 147.14 (C SB 2 sb ), 146.85-146.21 (m, Cq), 122.57-121.48 (m, Cq), 119.05 (dd, I J i = 18.9, 3.4 Hz, C SB 5 sb ), 118.93-114.64 (m, Cq), 119.00-105.00 (m, C SB CF sb ). SP 13 sp C NMR (75 MHz, acetone- I d i SB 6 sb ): = 159.91 (dt, I J i = 252.3, 5.2 Hz, C SB 6 sb ), 157.63 (d, I J i = 3.8 Hz, C SB 4 sb ), 147.42 (Cq), 146.79 (C SB 2 sb ), 133.10 (d, I J i = 7.3 Hz, Cq), 126.29-125.29 (m, C SB 5,7,8 sb ),, 123.00-105.00 (m, C SB CF sb ). [Extracted from the article]

We report the straightforward one‐pot synthesis of novel 5‐ or 6‐membered P‐heterocycles featuring an internal ylidic bond: P‐containing acenaphthylenes and phenanthrenes. The stability of the compounds tolerates post‐functionalization through direct arylation to introduce electron‐rich/poor substituents and the synthetic strategy is also compatible with the preparation of more elaborate polyaromatic scaffolds such as acenes and helicenes. Using a joint experimental (X‐ray analysis, optical and redox properties) and theoretical approach, we perform a full structure–property relationships study on these new platforms. In particular, we show that molecular engineering allows not only tuning their absorption/emission across the entire visible range but also endowing them with chiroptical or non‐linear optical properties, making them valuable dyes for a large panel of photonic or opto‐electronic applications. [ABSTRACT FROM AUTHOR]

We report the straightforward one‐pot synthesis of novel 5‐ or 6‐membered P‐heterocycles featuring an internal ylidic bond: P‐containing acenaphthylenes and phenanthrenes. The stability of the compounds tolerates post‐functionalization through direct arylation to introduce electron‐rich/poor substituents and the synthetic strategy is also compatible with the preparation of more elaborate polyaromatic scaffolds such as acenes and helicenes. Using a joint experimental (X‐ray analysis, optical and redox properties) and theoretical approach, we perform a full structure–property relationships study on these new platforms. In particular, we show that molecular engineering allows not only tuning their absorption/emission across the entire visible range but also endowing them with chiroptical or non‐linear optical properties, making them valuable dyes for a large panel of photonic or opto‐electronic applications. [ABSTRACT FROM AUTHOR]

We report a straightforward synthesis of Si-containing Polycyclic Aromatic Hydrocarbons (PAHs). The impact of π-extension and exocyclic modifications on both the optical and redox properties is investigated using a joint experimental/theoretical approach. By taking advantage of the solid-state luminescence of these derivatives, electroluminescent devices are prepared. Such preliminary opto-electronic results highlight that these heteroatom-containing PAHs are promising building blocks for organic electronics. [ABSTRACT FROM AUTHOR]

A family of cyclic phosphine‐disiloxane featuring peri‐substituted naphthyl(Nap)/acenaphthyl(Ace) scaffolds has been prepared and fully characterized including X‐ray structure, which enables a detailed structural analysis. This straightforward synthesis takes advantage of both ortho‐ and peri‐substitution of Nap/Ace‐substituted phosphine oxides. The synthetic method allows diversifying the polycyclic aromatic platform (Nap and Ace) as well as the Si substituents (Me and Ph). Despite a strong steric congestion, the P‐atom remains reactive toward oxidation or coordination. In particular, Au(I) complex could be prepared. All the compounds display absorption/luminescence in the UV‐Vis range. Surprisingly, the P‐trivalent derivatives display unexpected luminescence in the green in solid‐state. [ABSTRACT FROM AUTHOR]

In this article, we describe the synthesis of polyaromatic heteropines including main group element (Phosphorus, Germanium) through Ni or Cu‐mediated C−C coupling. Coordination complexes were synthesized with the σ3,λ3‐phosphepines using different metal ions (Au(I), Re(I), Pd(II)) showing that these P‐heterocycles display the classical reactivity of two‐electrons P‐donor making them promising ligands. The optical properties were experimentally studied (UV‐vis absorption and emission) and compared. Finally, both polyaromatic germepine and phosphepine appear as interesting building blocks for optoelectronics. [ABSTRACT FROM AUTHOR]

We report the straightforward synthesis of unprecedented electron‐acceptors based on dicationic P‐containing PAHs (Polycyclic Aromatic Hydrocarbons) based on copper mediated radical approach. In these systems, two phosphoniums are connected through various PAHs backbones. The impact of π‐extension on both the optical and redox properties is investigated using a joint experimental (UV/Vis absorption, fluorescence and cyclic voltammetry) and theoretical approach (TD‐DFT calculations). Finally, (spectro)‐electrochemical studies prove that these compounds possess three redox states and EPR studies confirm the in situ formation of an organic radical delocalized on the PAH backbone. [ABSTRACT FROM AUTHOR]

This article presents the synthesis of a new family of naphthyl‐fused phosphepines through Ni‐mediated C−C coupling. Interestingly, the chlorophosphine oxide intermediate shows strong resistance toward oxidation/hydrolysis owing to a combination of steric hindrance and pnictogen interactions. However, it can undergo substitution reactions under specific conditions. The optical/redox properties and the electronic structure of these new π‐systems were studied experimentally (UV/Vis absorption, emission, cyclic voltammetry) and computationally (TD‐DFT calculations, NICS investigation). Taking advantage of the luminescence of these derivatives, a blue‐emitting OLED has been prepared, highlighting that these novel π‐conjugated P‐heterocycles appear to be promising building blocks for solid‐state lighting applications. [ABSTRACT FROM AUTHOR]

[Display omitted] • Polycyclic Aromatic Hydrocarbons are important building blocks for optoelectronics. • Inserting main group elements in the backbone is a powerful molecular engineering tool. • Compounds featuring 5, 6 or 7-membered cycles including Si, Ge and Sn, are presented. • To achieve such challenge, innovative synthetic approaches have been developed. • Opto-electronic devices were prepared (OLEDs, OFETs). Polycyclic aromatic hydrocarbons (PAHs) are important organic building blocks for optoelectronic applications. Among the various molecular engineering strategies (π-extension, edge structure modification, exocyclic functionalization), this review will focus on the insertion of heavy group 14 elements (Si, Ge and Sn) into the polyaromatic backbone. The main synthetic approaches toward these compounds will be discussed. Their optical and redox properties will be described with a particular attention of the specific effect of the heteroatom. Finally, there insertion into optoelectronic devices will be highlighted. [ABSTRACT FROM AUTHOR]