Styrylbenzoquinoline dyads as a new type of fluorescing photochromes operating via [2 + 2] photocycloaddition mechanism: Optimization of the structure.

We synthesized and studied a novel bichromophoric dyad in which bridging methylene groups link two styrylbenzo[f]quinoline (SBQ) photochromes to a salicylic acid residue. The dyad was designed for use as a fluorescent P-type photochrome acting via a [2 + 2] photocycloaddition (PCA) reaction. Compared to previously studied dyads, a change in the attachment handle and shortening of the bridging groups resulted in simultaneous rise of the quantum yields of both fluorescence and PCA. Under light irradiation, two competitive reversible reactions occurred in the dyad. The first is photoisomerization between the trans- and cis- isomers of the SBQ moieties. The second is PCA. The latter process was predominant and resulted in the formation of the cyclobutane ring bearing two benzo[f]quinoline (BQ) groups. In the ground S0 state, NMR data and DFT calculations indicated the formation of folded dyad conformers whose structure is pre-organized for PCA due to π-stacking interactions of two SBQ moieties. In the excited dyad, steady-state and time-resolved nanosecond fluorescence spectroscopy revealed the formation of an excimer, which was assumed to be a precursor of cyclobutane. Due to the fluorescence properties of SBQ and BQ, both dyad and cyclobutane fluoresce and can serve as a color-correlated multicolor fluorescence photoswitch. A simple approach is proposed for predicting the relationship between the spectral properties of the dyad and cyclobutane, which are the open and closed isomers of a new type of photochromes. The approach uses the dependence of the position of the maximum of the absorption band of an aromatic compound on the size of the π-system, as well as the fact that the sizes of the π-systems of the dyad and cyclobutane are related by a simple relation.

[2+2] Photocycloaddition in a bichromophoric dyad: photochemical concerted forward reaction following Woodward-Hoffmann rules and photoinduced stepwise reverse reaction of the ring opening via predissociation.

A novel biphotochromic dyad with styrylbenzo[f]quinoline photochromes was designed and synthesized to study the [2+2] photocycloaddition (PCA) reaction leading to cyclobutane with two benzo[f]quinoline (BQ) substituents and the reverse four-membered ring opening reaction. In the dyad, PCA occurs in a concerted manner according to the Woodward-Hoffmann rules in the ππ* excited state after excitation of the whole conjugated π-system comprising the ethylene group. Nanosecond time-resolved emission spectroscopy indicated formation of an excimer as a possible intermediate of the PCA reaction. The reverse reaction of photoinduced cyclobutane ring opening is assumed to proceed stepwise according to the predissociation mechanism: after excitation of the BQ substituent, energy transfer (ET) occurs from the bonding ππ* term localized on the BQ substituent to the dissociative πσ* term localized on cyclobutane; the efficiency of such a process was measured for the first time. For the first time, it is suggested that the predissociation mechanism is common to the ring-opening reaction of any cyclobutane with an unsaturated substituent where the π-system of the substituent rather than the σ-system of cyclobutane is excited under light irradiation.

Emissive and reactive excimers in a covalently-linked supramolecular multi-chromophoric system with a balanced rigid-flexible structure.

A novel multi-chromophoric system, triad, in which two styrylbenzoquinoline (SBQ) photochromes are connected by a balanced rigid-flexible linker comprising 2,3-naphthylene framework (a residue of 3-oxy-2-naphthoic acid) and tetramethylene groups, was designed and synthesized to study an excimer formation in the excited state. The 1H NMR data testified that triad exists in solution as folded conformers with asymmetric parallel-displaced SBQ units. Under light irradiation, in the triad, competitive photoisomerization and [2 + 2] photocycloaddition reactions were observed, both reactions being reversible. The photocycloaddition resulted in a tetrasubstituted cyclobutane. The red-shifted fluorescence spectrum and the appearance of a long-lived component in the triad fluorescence decay indicated formation of an 'emissive' excimer. The photocycloaddition is assumed to occur in a 'reactive' excimer, in which the ethylene groups of the SBQ photochromes are located at a distance sufficient for the formation of the σ-bonds between them. Quantum-chemical density functional theory (DFT) calculations at M06-2X/6-31G* level predicted the existence of the triad conformers with π-stacking interaction of SBQ photochromes, the structure of which is pre-organized for the excimer formation and photocycloaddition. For the first time, both emissive and reactive excimers were experimentally observed in the multi-chromophoric system with two diarylethylene photochromes undergoing [2 + 2] photocycloaddition.

Semiempirical study on the absorption spectra of the coronene-like molecular models of graphene quantum dots.

Polycyclic aromatic hydrocarbons of the general formula C6n2H6n (coronene family) were used as molecular models of graphene quantum dots (GQDs). Absorption spectra of the model compounds were calculated by ZINDO/S method. The S0 → S1 transition energy (E1) was found to decrease with n as E1 = 4.75 × n-0.633 eV. This transition is forbidden in symmetric compounds but 'switches on' upon symmetry breaking. The energy of the first bright optical peak (Ebr) was found to decrease with n as Ebr = 6.31 × n-0.6 eV. The data obtained corroborate the earlier finding that the size-independent optical properties of GQDs are determined by relatively small isolated sp2 clusters separated by sp3 (oxygen-contained) 'defects' rather than the whole (corrupted) graphene sheets; such nanoparticles actually are not quantum dots. GQDs of pure (without defects) graphene sheets with fully π-conjugated sp2 systems should exhibit size-dependent optical properties due to the quantum confinement effect.

Visible-light-driven two-way photoisomerization of 1-(1-pyrenyl)-2-(2-quinolyl)ethylene in neutral and protonated forms.

Diarylethylenes with large π-systems often lose their photochemical activity (the size effect). 1-(1-Pyrenyl)-2-(2-quinolyl)ethylene (1P2QE), despite having a large conjugated π-system of 28 electrons, undergoes two-way reversible trans-cis photoisomerization both in the neutral and protonated forms with quantum yields as high as 0.13-0.83. For the neutral 1P2QE, experimental data and quantum-chemical calculations indicate a diabatic (nonadiabatic) reaction mechanism. Due to high photoisomerization quantum yields and the long-wavelength absorption band at 340-460 nm and 390-560 nm for the neutral and protonated compounds, respectively, 1P2QE can be used as a molecular photoswitch that is sensitive to visible light.

Spectral and photochemical properties of hybrid organic-inorganic nanosystems based on CdS quantum dots and merocyanine ligands.

The spectral and photochemical properties of hybrid organic-inorganic nanosystems (HNSs) were investigated. HNS consisted of CdS quantum dots (QDs) functionalized with ligands containing the isothiouronium anchor group linked by a polymethylene chain with photochromic merocyanine (MC). The HNS synthesis was carried out via a microwave-assisted one-pot technique. Energy transfer from the QDs to MC in the HNS was observed and resulted in QD fluorescence quenching and MC sensitization. Compared to the free MC, trans-cis photoisomerization of MC in the HNS was suppressed and its photodestruction was accelerated. In addition, upon HNS photolysis by visible light with energy higher than the threshold, the photosensitized destruction of the QDs (which did not absorb the applied light) occurred. The observed effects were proposed to be caused by MC adsorption on QDs surface, which leads to the restriction of the MC photoisomerization and population of the surface electron trap states of the QDs.

Multifunctional Photonic Molecular Logic Gate Based On A Biphotochromic Dyad With Reduced Energy Transfer.

Using molecular logic gates (MLGs) for information processing attracts attention due to perspectives of creating molecular computers. Biphotochromic dyads are suitable models of photonic MLGs. However, they suffer from one weakness: the activity of one of the photochromes is often quenched because of Förster resonance energy transfer (FRET). Herein, we designed a dyad with reduced FRET, in which both photochromes keep their photoactivity thanks to spectral and spatial separation, allowing MLG switching between different states. This novel dyad reproduces the functionality of the full set of 16 two-input gates, as well a reversible gate-dual inverter, all gates are photonic.

EPR studies on branched high-spin arylnitrenes.

The UV (λ>305 nm) photolysis of triazide 3 in 2-methyl-tetrahydrofuran glass at 7 K selectively produces triplet mononitrene 4 (g=2.003, D(T)=0.92 cm(-1), E(T)=0 cm(-1)), quintet dinitrene 6 (g=2.003, D(Q)=0.204 cm(-1), E(Q)=0.035 cm(-1)), and septet trinitrene 8 (g=2.003, D(S)=-0.0904 cm(-1), E(S) =-0.0102 cm(-1)). After 45 min of irradiation, the major products are dinitrene 6 and trinitrene 8 in a ratio of ∼1:2, respectively. These nitrenes are formed as mixtures of rotational isomers each of which has slightly different magnetic parameters D and E. The best agreement between the line-shape spectral simulations and the experimental electron paramagnetic resonance (EPR) spectrum is obtained with the line-broadening parameters Γ(E(Q))=180 MHz for dinitrene 6 and Γ(E(S))=330 MHz for trinitrene 8. According to these line-broadening parameters, the variations of the angles Θ in rotational isomers of 6 and 8 are expected to be about ±1 and ±3°, respectively. Theoretical estimations of the magnetic parameters obtained from PBE/DZ(COSMO)//UB3LYP/6-311+G(d,p) calculations overestimate the E and D values by 1 and 8 %, respectively. Despite the large distances between the nitrene units and the extended π systems, the zero field splitting (zfs) parameters D are found to be close to those in quintet dinitrenes and septet trinitrenes, where the nitrene centers are attached to the same aryl ring. The large D values of branched septet nitrenes are due to strong negative one-center spin-spin interactions in combination with weak positive two-center spin-spin interactions, as predicted by theoretical considerations.

Strain effects in electron spin resonance spectroscopy of quintet 2,6-bis(4'-nitrenophenyl)-4-phenylpyridine.

Photolysis of 2,6-bis(4'-azidophenyl)-4-phenylpyridine in 2-methyltetrahydrofuran (2MTHF) glass at 7 K leads to quintet 2,6-bis(4'-nitrenophenyl)-4-phenylpyridine as a mixture of rotational isomers. The electron spin resonance (ESR) spectrum of this mixture of rotamers shows a considerable broadening of many transitions in the range of 0-5000 G and cannot be reproduced by computer simulations solely based on the tuning of the spin Hamiltonian parameters g, D(Q), and E(Q) alone or on predictions of DFT calculations. The best modeling of the experimental ESR spectrum is obtained only when the large line-broadening parameter of Γ(E(Q)) = 1200 MHz along with the spin Hamiltonian g = 2.003, D(Q) = 0.154 cm(-1), and E(Q) = 0.050 cm(-1) is used in the spectral simulations. The most accurate theoretical estimations of the magnetic parameters of the dinitrene in a 2MTHF glass are obtained from the B3LYP/6-311+G(d,p)+PBE/DZ/COSMO calculations of the spin-spin coupling parameters D(SS) and E(SS). Such calculations overestimate the E(Q) and D(Q) values of the dinitrene just by 1% and 10%, respectively, demonstrating that contributions of the spin-orbit coupling parameters D(SOC) and E(SOC) to the total D(Q) and E(Q) values are negligibly small. The research shows that ESR studies of polynuclear high-spin nitrenes, obtained by photolysis of rotational isomers of the starting azides, can only be successful if large E(Q) strain effects are taken into account in the spectral simulations.