Emissive supramolecular ionic crystals combining a red-NIR phosphorescent [Re6Se8CN6]4- cluster anion and a blue fluorescent tetraphenylethene counter-cation.

A blue fluorescent tetraphenylethylene-based dication and a red-NIR phosphorescent rhenium octahedral cluster tetra-anion are associated electrostatically to generate a supramolecular ionic framework which crystallizes in the P1̄ centric space group. The emission properties of the hybrids are studied in the crystalline state and in solution revealing a resonant energy transfer and a high sensitivity toward oxygen.

Phosphetene-based polyaromatics: structure-property relationships and chiroptical tuning.

We describe the synthesis of π-extended phosphetene rings (4-member P-rings) flanked with PAH systems of various topologies. These compounds are fully characterized including X-ray diffraction. The impact of both the polyaromatic platform and the P-ring on the structure, and the optical and redox properties are investigated both experimentally and theoretically. Although neither the P centre nor the 4-membered ring significantly takes part in the HOMO or LUMO orbitals, both structural features have an important modulating role in distorting the symmetry of the orbitals, leading to chiroptical properties. The stereogenic P-atom is used as a remote chiral perturbator to induce circularly polarized luminescence of the polyaromatic system. The dissymmetry factor is highly dependent on the polyaromatic topology, as supported by theoretical calculations.

Dithieno[2,3-b;3,2-f]phosphepinium-Based Near-Infrared Fluorophores: px-π* Conjugation Inherent to Seven-Membered Phosphacycles.

Positively charged phosphorus-containing heterocycles are characteristic core skeletons for functional molecules. While various phosphonium-containing five- or six-membered ring compounds have been reported, seven-membered ring phosphepinium has not yet been fully studied. In this study, dithieno[2,3-b;3,2-f]phosphepinium ions containing electron-donating aminophenyl groups were synthesized. An X-ray crystallographic analysis of the resulting donor-acceptor-donor dyes revealed a bent conformation of the central seven-membered ring. This compound exhibited fluorescence in the near-infrared region with a bathochromic shift of 70 nm compared to phosphepine oxide congener and a large Stokes shift. High fluorescence quantum yields were obtained even in polar solvents due to the suppression of the nonradiative decay process. The theoretical study revealed that the phosphepinium skeleton is highly electron-accepting owing to the orbital interaction between a px orbital of the phosphonium moiety and a π* orbital of the 1,3,5-hexatriene moiety. Owing to the lower-lying px orbital in the phosphonium moiety compared with that of the phosphine oxide and the bent conformation of the seven-membered ring, the phosphepinium ring effectively furnishes a px-π* conjugation. A large structural relaxation with the contribution of a quinoidal resonance structure is suggested in the excited state, which is responsible for the intense emission with a large Stokes shift.

Molecular engineering of 3-arylated tetrazo[1,2-b]indazoles: divergent synthesis and structure-property relationships.

The synthetic scope of 3-arylated tetrazo[1,2-b]indazoles is reported based on a Pd-catalyzed Liebeskind-Srogl cross-coupling reaction followed by an N-cyclisation process. The reactivity of the nitrogen atoms was used to further diversify these N-rich polyaromatic tetrazo[1,2-b]indazoles in a panel of reactions (protonation, selective oxidation, metallations). Selective ortho-C-H activation/functionalization on the heterocycle was also demonstrated with three transition metals (TM = Pd, Ir and Rh). The effects of all these molecular engineering strategies, particularly the N-modifications, on the optical and redox properties of the 3-arylated tetrazoindazoles were studied experimentally and theoretically. This study highlights the diversity of molecular structures and electronic properties offered by the tetrazo[1,2-b]indazole platform.

Luminescent Supramolecular Ionic Frameworks based on Organic Fluorescent Polycations and Polyanionic Phosphorescent Metal Clusters.

Emissive ionic supramolecular frameworks are designed by associating tetraphenylethylene-based tetra-cationic units and di-anionic molybdenum or tetra-anionic rhenium octahedral clusters. Obtained structures were characterized by single-crystal X-ray diffraction. The emission properties of the hybrids were investigated as dry powders or in various solvents by one photon and two photon absorption leading to a O2 concentration dependent luminescence color for the Mo based hybrid.

Phospha-cyanines in Their Ideal Polymethine State: Synthesis and Structure-Property Relationships.

We report the synthesis and full characterization of a family of phosphorus-containing polymethine cyanines (phospha-cyanines). The compounds are easily prepared in two steps, starting from readily available phosphanes. The impact of the P-substituents and the counterions on the structural and optical properties is investigated through a joint experimental/theoretical approach. Based on the study of the single-crystal X-ray diffraction structures, all phospha-cyanines present a bond length alternation close to zero, independently of the substituents and counterions, which indicates an ideal polymethine state. All these compounds display the typical cyanine-like UV-vis absorption with an intense and sharp transition with a vibronic shoulder despite possessing a reverse electronic configuration compared to "classical" cyanines. Time-dependent density-functional theory calculations allowed us to fully rationalize the optical properties (absorption/emission wavelengths, luminescence quantum yields). Interestingly, due to the tetrahedral shape of the P atom, the optical properties are independent of the counterion, which is in marked contrast with N-analogues, which enables predictive engineering of the phospha-cyanines regardless of the medium in which they are used.

Intrinsically Switchable Electroactive Fluorophores Based on λ5 -Biphosphinines.

The synthesis and full characterization of a family of stable λ5 -biphosphinines connected in 4,4-position through a variety of π-conjugated bridges is reported. The impact of the π-bridge on the optical (absorption/emission) and redox properties was investigated using a joint experimental/theoretical approach. In contrast to the π-extended ones, the λ5 -biphosphinines directly connected through a C-C bond in 4,4-position display two easily accessible and reversible oxidations highlighting their multi-stage redox character. The in situ formed radical cations are studied by spectro-electrochemistry and electron paramagnetic resonance. Finally, electrochemical modulation of fluorescence (electrofluorochromism) was performed and revealed the potential of these intrinsically switchable electroactive fluorophores for further applications as switchable materials.

Tetrazo[1,2-b]indazoles: Straightforward Access to Nitrogen-Rich Polyaromatics from s-Tetrazines.

The straightforward access to a new class of aza-polyaromatics is reported. Starting from readily available fluorinated s-tetrazine, a cyclization process with azide leads to the formation of an unprecedented tetrazo[1,2-b]indazole or a bis-tetrazo[1,2-b]indazole (cis and trans conformers). Based on the new nitrogen core, further N-directed palladium-catalyzed ortho-C-H bond functionalization allows the introduction of halides or acetates. The physicochemical properties of these compounds were studied by a joint experimental/theoretical approach. The tetrazo[1,2-b]indazoles display solid-state π-stacking, low reduction potential, absorption in the visible range up to the near-infrared, and intense fluorescence, depending on the molecular structure.

Tuning the Charge Transfer in λ5-Phosphinines with Amino Substituents.

We report the substitution of λ5-phosphinines (2,6-dicarbonitrile diphenyl-1-λ5-phosphinine) with an amino group. The impact of these modifications on both the optical and redox properties is investigated using a joint experimental/theoretical approach. In particular, we show that the choice of the donor diphenylamino group dramatically impacts the nature of the charge transfer. The use of di(methoxyphenyl)amine redshifts the optical properties and allows thermally activated delayed fluorescence in the solid state. Finally, we demonstrated that λ5-phosphinines with an amino group can be used as active emitters in an electroluminescent device.

Straightforward Access to Multifunctional π-Conjugated P-Heterocycles Featuring an Internal Ylidic Bond.

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.

Si-containing polycyclic aromatic hydrocarbons: synthesis and opto-electronic properties.

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.

Stereospecific synthesis of chiral P-containing polyaromatics based on 7-membered P-rings.

We present the stereospecific synthesis of helicenoid-based phosphepines (7-membered P-rings) as well as chiral P-containing polycyclic aromatic hydrocarbons. In these systems, an axial to central chirality transfer takes place from the BINAP moiety to the P-atom. The impact of the molecular design on the structure, the (chir)optical (including circularly polarized luminescence) and redox properties are investigated.

Taking Advantage of Ortho- and Peri-Substitution to Design Nine-Membered P,O,Si-heterocycles*.

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.

[n]-Cyclo-9,9-dibutyl-2,7-fluorene (n=4, 5): Nanoring Size Influence in Carbon-Bridged Cyclo-para-phenylenes.

For the last ten years, ring-shaped π-conjugated macrocycles possessing radially directed π-orbitals have been subject to intense research. The electronic properties of these rings are deeply dependent on their size. However, most studies involve the flagship family of nanorings: the cyclo-para-phenylenes. We report herein the synthesis and study of the first examples of cyclofluorenes possessing five constituting fluorene units. The structural, optical and electrochemical properties were elucidated by X-ray crystallography, UV-vis absorption and fluorescence spectroscopy, and cyclic voltammetry. By comparison with a shorter analogue, we show how the electronic properties of [5]-cyclofluorenes are drastically different from those of [4]-cyclofluorenes, highlighting the key role played by the ring size in the cyclofluorene family.

Multi-Stage Redox Systems Based on Dicationic P-Containing Polycyclic Aromatic Hydrocarbons.

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.

Naphthyl-Fused Phosphepines: Luminescent Contorted Polycyclic P-Heterocycles.

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.

π-Extended Phosphepines: Redox and Optically Active P-Heterocycles with Nonplanar Framework.

In this letter, we present the synthesis of a new family of π-extended dithieno[ b, f]phosphepines. The Pd-catalyzed direct arylation allows the introduction of various substituents, which tune the absorption/emission in the visible range as well as the redox properties. All those modifications were rationalized through DFT calculations. The physical properties of ambipolar phosphepine with diphenylamino substituents inspired us to use it as a semiconductor in p-type organic field-effect transistors (OFETs).

Strong Solid-state Luminescence Enhancement in Supramolecular Assemblies of Polyoxometalate and "Aggregation-Induced Emission"-active Phospholium.

Two new supramolecular fluorescent hybrid materials, combining for the first time [M6 O19 ]2- (M=Mo, W) polyoxometalates (POMs) and aggregation-induced emission (AIE)-active 1-methyl-1,2,3,4,5-pentaphenyl-phospholium (1+ ), were successfully synthesized. This novel molecular self-assembling strategy allows designing efficient solid-state emitters, such as (1)2 [W6 O19 ], by directing favorably the balance between the AIE and aggregation-caused quenching (ACQ) effects using both anion-π+ and H-bonding interactions in the solid state. Combined single-crystal X-ray diffraction, Raman, UV-vis and photoluminescence analyses highlighted that the nucleophilic oxygen-enriched POM surfaces strengthened the rigidity of the phospholium via strong C-H⋅⋅⋅O contacts, thereby exalting its solid-state luminescence. Besides, the bulky POM anions prevented π-π stacking interactions between the luminophores, blocking detrimental self-quenching effects.

Synthesis, Optical, and Redox Properties of Regioisomeric Benzoheterocycles-Fused Pyrene.

A new synthetic route toward the synthesis of benzo[b]phospholes- and benzo[b]siloles-fused pyrenes using a transition metal-catalyzed C-H bond activation is described. The compounds were fully characterized including X-ray diffraction. A combined experimental and theoretical study shows that both the heteroatom and the substitution pattern impact the optical and redox properties.

Calix[4]arene-fused phospholes.

An upper rim, o-(diphenylphosphinyl)phenyl-substituted calix[4]arene has been prepared and its coordinative properties investigated. When heated in the presence of palladium, the new biarylphosphine undergoes conversion into two diastereomeric, calixarene-fused phospholes. In both, the P lone pair adopts a fixed orientation with respect to the calixarene core. The more hindered phosphole (8), i.e. the one with the endo-oriented lone pair (cone angle 150°-175°), forms complexes having their metal centre positioned very near the calixarene unit but outside the cavity, thus inducing an unusual chemical shift of one of the methylenic ArCH2Ar protons owing to interactions with the metal centre. As expected for dibenzophospholes, the complex [Rh(acac)(CO)·8], when combined with one equivalent of free 8, efficiently catalyses the hydroformylation of styrene, the catalytic system displaying high regioselectivity in favour of the branched aldehyde (b/l ratio up to 30). The optical and redox properties of the derivatives have also been investigated.