How To Make Nitroaromatic Compounds Glow: Next-Generation Large X-Shaped, Centrosymmetric Diketopyrrolopyrroles.

Red-emissive π-expanded diketopyrrolopyrroles (DPPs) with fluorescence reaching λ=750 nm can be easily synthesized by a three-step strategy involving the preparation of diketopyrrolopyrrole followed by N-arylation and subsequent intramolecular palladium-catalyzed direct arylation. Comprehensive spectroscopic assays combined with first-principles calculations corroborated that both N-arylated and fused DPPs reach a locally excited (S1 ) state after excitation, followed by internal conversion to states with solvent and structural relaxation, before eventually undergoing intersystem crossing. Only the structurally relaxed state is fluorescent, with lifetimes in the range of several nanoseconds and tens of picoseconds in nonpolar and polar solvents, respectively. The lifetimes correlate with the fluorescence quantum yields, which range from 6 % to 88 % in nonpolar solvents and from 0.4 % and 3.2 % in polar solvents. A very inefficient (T1 ) population is responsible for fluorescence quantum yields as high as 88 % for the fully fused DPP in polar solvents.

N-Arylation of Diketopyrrolopyrroles with Aryl Triflates.

A new methodology for the double N-arylation of diketopyrrolopyrroles with aryl triflates has been developed. It is now possible to prepare diketopyrrolopyrroles bearing N-substituents derived from naphthalene, anthracene and coumarin in two steps from commercially available phenols. This represents the first time arenes lacking strong electron-withdrawing groups were inserted onto lactamic nitrogen atoms via arylation. The ability to incorporate heretofore unprecedented substituents translates to increased modulation of the resulting photophysical properties such as switching-on/off solvatofluorochromism. TD-DFT calculations have been performed to explore the nature of the relevant excited states. This new synthetic method made it possible to elucidate the influence of such substituents on the absorption and emission properties of tetraaryl substituted diketopyrrolopyrroles.

Gating That Suppresses Charge Recombination-The Role of Mono-N-Arylated Diketopyrrolopyrrole.

Suppressing the charge recombination (CR) that follows an efficient charge separation (CS) is of key importance for energy, electronics, and photonics applications. We focus on the role of dynamic gating for impeding CR in a molecular rotor, comprising an electron donor and acceptor directly linked via a single bond. The media viscosity has an unusual dual effect on the dynamics of CS and CR in this dyad. For solvents with intermediate viscosity, CR is 1.5-3 times slower than CS. Lowering the viscosity below ∼0.6 mPa s or increasing it above ∼10 mPa s makes CR 10-30 times slower than CS. Ring rotation around the donor-acceptor bond can account only for the trends observed for nonviscous solvents. Media viscosity, however, affects not only torsional but also vibrational modes. Suppressing predominantly slow vibrational modes by viscous solvents can impact the rates of CS and CR to a different extent. That is, an increase in the viscosity can plausibly suppress modes that are involved in the transition from the charge-transfer (CT) to the ground state, i.e., CR, but at the same time are not important for the transition from the locally excited to the CT state, i.e., CS. These results provide a unique example of synergy between torsional and vibronic modes and their drastic effects on charge-transfer dynamics, thus setting paradigms for controlling CS and CR.

Light-Induced Direct Arylation in the Solid Crystalline State as a Strategy Towards π-Expanded Imidazoles.

π-Expanded imidazoles bearing the 2-iodophenyl substituent at position 2 undergo direct photoinduced intramolecular arylation in the solid, crystalline state leading to large non-planar heterocycles. An analogous reaction employing 2-bromophenyl and 2-chlorophenyl substituents is considerably slower. Such processes have never before been demonstrated to occur in crystals and have allowed the efficient synthesizes of structurally unique compounds containing either the phenanthro[9',10':4,5]imidazo[1,2-f]phenanthridine moiety or structurally related skeletons. The reaction occurs in the thin crystalline layers irradiated with UV photons in an almost quantitative manner over 48-72 h. Several previously unknown architectures have been prepared using this methodology. Furthermore, the optical properties of these π-expanded imidazoles can be altered with the addition of heteroatoms and/or electron-donating groups.

How To Reach Intense Luminescence for Compounds Capable of Excited-State Intramolecular Proton Transfer?

Photoinduced intramolecular direct arylation allows structurally unique compounds containing phenanthro[9',10':4,5]imidazo[1,2-f]phenanthridine and imidazo[1,2-f]phenanthridine skeletons, which mediate excited-state intramolecular proton transfer (ESIPT), to be efficiently synthesized. The developed polycyclic aromatics demonstrate that the combination of five-membered ring structures with a rigid arrangement between a proton donor and a proton acceptor provides a means for attaining large fluorescence quantum yields, exceeding 0.5, even in protic solvents. Steady-state and time-resolved UV/Vis spectroscopy reveals that, upon photoexcitation, the prepared protic heteroaromatics undergo ESIPT, converting them efficiently into their excited-state keto tautomers, which have lifetimes ranging from about 5 to 10 ns. The rigidity of their structures, which suppresses nonradiative decay pathways, is believed to be the underlying reason for the nanosecond lifetimes of these singlet excited states and the observed high fluorescence quantum yields. Hydrogen bonding with protic solvents does not interfere with the excited-state dynamics and, as a result, there is no difference between the occurrences of ESIPT processes in MeOH versus cyclohexane. Acidic media has a more dramatic effect on suppressing ESIPT by protonating the proton acceptor. As a result, in the presence of an acid, a larger proportion of the fluorescence of ESIPT-capable compounds originates from their enol excited states.

Photochemical Conversion of Phenanthro[9,10-d]imidazoles into π-Expanded Heterocycles.

We discovered that phenanthro[9,10-d]imidazoles bearing a 2-halogenoaryl substituent at position 2 undergo swift photochemically driven direct arylation, leading to barely known phenanthro[9',10':4,5]imidazo[1,2-f]phenanthridines. The reaction is high-yielding, and it does not require any sensitizer or base. The discovered process is tolerant of a variety of substituents present both at positions 1 and 2; i.e., strongly electron-donating and electron-withdrawing substituents are tolerated as well as various heterocyclic units. Steric hindrance does not affect this process. The evidence gathered here indicates that SRN1 mechanism is operating in this case with the formation of radical anion as a critical step, followed by heterolytic cleavage of a carbon-halogen bond. Also TfO groups were shown to undergo cyclization, which allows the use of salicylaldehydes in the construction of heterocyclic systems. Efficiency of this photochemically driven direct arylation has been demonstrated by the synthesis of two systems possessing 13 and 17 conjugated rings, respectively. Phenanthro[9',10':4,5]imidazo[1,2-f]phenanthridines are blue-emitters, and they exhibit strong fluorescence in solution and in the solid state in direct contrast to their precursors.

Blue-green emitting sulphonamido-imidazole derivatives: ESIPT based excited state dynamics.

Six imidazole derivatives characterized by the presence in their molecules of a sulphonamido group and able to display excited state intramolecular proton transfer (ESIPT) have been synthesized in a straightforward manner and the dynamics of their excited states investigated in detail in solvents of different polarity and proticity: toluene (TOL), dichloromethane (DCM) and methanol (MeOH). With the exception of one compound, these ESIPT-capable molecules are highly luminescent. The major emitting species at room temperature is the ketimine (K) tautomer but the weak emission from the enamide (E) form was detected in several cases. In general, the luminescence quantum yields (φfl) of the K form range between 0.4 and 0.6 with lifetimes of several nanoseconds, with radiative rate constants kr of the order of 10(8) s(-1). The lifetime of the E form, and hence of the ESIPT process, range between τ <10 ps up to 190 ps. At 77 K, in addition to hypsochromically shifted fluorescence bands from the E and/or K tautomers, E phosphorescence emissions with lifetimes in the range of seconds (0.4-2.5 s) are also detected. The triplet excited state absorbance of these molecules was probed in DCM and MeOH and both E (between 450-520 nm) and K (at about 420 nm) forms were identified. The triplet lifetimes at room temperature in air-free solutions are in the microsecond range, whereas the reaction rates with oxygen are of the order of 10(9) M(-1) s(-1).

Comparison of oxidative aromatic coupling and the Scholl reaction.

Does the dehydrogenative coupling of aromatic compounds mediated by AlCl3 at high temperatures and also by FeCl3, MoCl5, PIFA, or K3[Fe(CN)6] at room temperature proceed by the same mechanism in all cases? With the growing importance of the synthesis of aromatic compounds by double C-H activation to give various biaryl structures, this question becomes pressing. Since some of these reactions proceed only in the presence of non-oxidizing Lewis acids and some only in the presence of certain oxidants, the authors venture the hypothesis that, depending on the electronic structure of the substrates and the nature of the "catalyst", two different mechanisms can operate. One involves the intermediacy of a radical cation and the other the formation of a sigma complex between the acid and the substrate. The goal of this Review is to encourage further mechanistic studies hopefully leading to an in-depth understanding of this phenomenon.

Calix[4]pyrroles bearing proximally meso-meso linking straps: synthesis and anion binding properties.

Calix[4]pyrroles bearing two proximally crossing straps on the same or the opposite sides have been synthesized for the first time. The doubly cis-strapped compound exhibited highly cooperative six-point hydrogen bonding interactions with the anion involving both pyrrolic N-Hs and Ar-Hs.