Falk Renth

Highly Efficient Reversible Z−E Photoisomerization of a Bridged Azobenzene with Visible Light through Resolved S1(nπ*) Absorption Bands

The reversible Z-E photoswitching properties of the (Z) and (E) isomers of the severely constrained bridged azobenzene derivative 5,6-dihydrodibenzo[c,g][1,2]diazocine (1) were investigated quantitatively by UV/vis absorption spectroscopy in solution in n-hexane. In contrast to normal azobenzene (AB), 1 has well separated S(1)(n pi*) absorption bands, peaking at lambda(Z) = 404 nm and lambda(E) = 490 nm. Using light at lambda = 385 nm, it was found that 1Z can be switched to 1E with very high efficiency, Gamma = 92 +/- 3%. Conversely, 1E can be switched back to 1Z using light at lambda = 520 nm with approximately 100% yield. The measured quantum yields are Phi(Z-->E) = 72 +/- 4% and Phi(E-->Z) = 50 +/- 10%. The thermal lifetime of the (E) isomer is 4.5 +/- 0.1 h at 28.5 degrees C. The observed photochromic and photoswitching properties of 1 are much more favorable than those for normal AB, making our title compound a promising candidate for interesting applications as a molecular photoswitch especially at low temperatures. The severe constraints by the ethylenic bridge apparently do not hinder but favor the Z-E photoisomerization reactions.

Photofragment velocity map imaging of H atom elimination in the first excited state of pyrrole

Photofragment velocity map imaging was used to study the H atom elimination mechanism in the first excited state of pyrrole at λ=243.1 nm. Two major channels were observed. The first one (76%) produces very fast H atoms and appears to be due to a rapid direct N–H bond breaking in the excited electronic state. The respective H atom kinetic energy distribution has a strong narrow peak at high energies, showing that ≈72% of the available energy is transferred into relative fragment translation. The observed angular recoil distribution which is described by an anisotropy parameter of β=−0.37±0.05 indicates that the excited optical transition is preferentially perpendicular with respect to the N–H dissociation coordinate. From the maximal kinetic energy release, the value of the N–H bond dissociation energy was found to be D0(N–H)=(32400±400) cm−1. The other channel (24%) leads to much slower H atoms with a very broad kinetic energy distribution, consistent with subsequent unimolecular decay reactions of the molecules in the ground electronic state after internal conversion. This conclusion was supported by similar experiments for N-methylpyrrole which showed only H atoms from the second channel and no fast component. The results corroborate the conclusion that the lowest electronic state of pyrrole has πσ* anti-bonding character and is repulsive with respect to the stretching of the N–H bond.

Superior Z→E and E→Z photoswitching dynamics of dihydrodibenzodiazocine, a bridged azobenzene, by S1(nπ*) excitation at λ = 387 and 490 nm.

The ultrafast Z→E and E→Z photoisomerisation dynamics of 5,6-dihydrodibenzo[c,g][1,2]diazocine (1), the parent compound of a class of bridged azobenzene-based photochromic molecular switches with a severely constrained eight-membered heterocyclic ring as central unit, have been studied by femtosecond time-resolved spectroscopy in n-hexane as solvent and by quantum chemical calculations. The diazocine contrasts with azobenzene (AB) in that its Z rather than E isomer is the energetically more stable form. Moreover, it stands out compared to AB for the spectrally well separated S(1)(nπ*) absorption bands of its two isomers. The Z isomer absorbs at around λ = 404 nm, the E form has its absorption maximum around λ = 490 nm. The observed transient spectra following S(1)(nπ*) photoexcitation show ultrafast excited-state decays with time constants τ(1) = 70 fs for the Z and <50 fs for the E isomer reflecting very fast departures of the excited wave packets from the S(1) Franck-Condon regions and τ(2) = 270 fs (320 fs) related to the Z→E (resp. E→Z) isomerisations. Slower transient absorption changes on the time scale of τ(3) = 5 ps are due to vibrational cooling of the reaction products. The results show that the unique steric constraints in the diazocine do not hinder, but accelerate the molecular isomerisation dynamics and increase the photoswitching efficiencies, contrary to chemical intuition. The observed isomerisation times and quantum yields are rationalised on the basis of CASPT2//CASSCF calculations by a S(1)/S(0) conical intersection seam at a CNNC dihedral angle of ≈96° involving twisting and torsion of the central CNNC moiety. With improved photochromism, high quantum yields, short reaction times and good photostability, diazocine 1 and its derivatives constitute outstanding candidates for photoswitchable molecular tweezers and other applications.

Enhanced photoswitching and ultrafast dynamics in structurally modified photochromic fulgides

Emerging new applications, e.g. as molecular logical devices and in superresolution imaging, have fuelled considerable interest in the design of improved fulgide photoswitches and the fundamental ultrafast processes that determine their photochemistry. This review is concerned with the basic photoswitching properties of fulgides and fulgimides. The emphasis is put on recent results on the underlying photoinduced ultrafast dynamics of chemically modified fulgides to uncover the basis for the observed changes in the photochemical behaviour upon structural variation. Particular attention is directed at the effects of selected structural motifs on the photoisomerisation pathways and the implications for a rational design of derivatives with improved switching properties.

Inversion of velocity map ion images using iterative regularization and cross validation

Two methods for improved inversion of velocity map images are presented. Both schemes use two-dimensional basis functions to perform the iteratively regularized inversion of the imaging equation in matrix form. The quality of the reconstructions is improved by taking into account the constraints that are derived from prior knowledge about the experimental data, such as non-negativity and noise statistics, using (i) the projected Landweber [Am. J. Math. 73, 615 (1951)] and (ii) the Richardson-Lucy [J. Opt. Soc. Am. 62, 55 (1972); Astron. J. 79, 745 (1974)] algorithms. It is shown that the optimum iteration count, which plays the role of a regularization parameter, can be determined by partitioning the image into quarters or halves and a subsequent cross validation of the inversion results. The methods are tested with various synthetic velocity map images and with velocity map images of the H-atom fragments produced in the photodissociation of HBr at λ=243.1nm using a (2+1) resonantly enhanced multiphoton i...

Tuning of switching properties and excited-state dynamics of fulgides by structural modifications

The ultrafast photo-induced dynamics of the E-isomers of four selected photochromic fulgides with distinct structural motifs have been elucidated by femtosecond broadband transient absorption spectroscopy in n-hexane as solvent. E→C and E→Z isomerisations, respectively, with time constants of ∼0.12 ± 0.02 ps and ∼0.34 ± 0.03 ps taking place in parallel were found for derivatives with a methyl substituent at the central hexatriene (HT) unit. In contrast, fulgides with increased steric constraints by an iso-propyl substituent or by intramolecular bridging displayed virtually zero E→Z isomerisation, but instead a desired accelerated and more efficient ring closure in a reaction time of only ∼50 ± 10 fs. Both photoisomerisations appear to follow excited-state pathways with distinctive conical intersections. For the ring closure, direct barrierless pathways with steep downhill gradients are likely. Furthermore, the results indicate conformer-specific reactions, with ring closure exclusively by the E(α) conformer and E→Z isomerisation predominantly by the E(β) conformer, because the E(α)→Z channel is unfavoured by the faster and kinetically more competitive E(α)→C reaction. DFT calculations of the equilibrium structures showed that the sterically demanding groups at the HT unit shift the conformer equilibria towards the E(α) conformers. At the same time, they appear to cause a favourable pre-orientation of the furyl unit that accelerates the conrotatory ring closure in the E(α)→C reaction. Benzo-annulation of the furyl unit has little effect on the observed dynamics. Overall, the results demonstrate how the excited-state dynamics and thereby the photoswitching properties of fulgides can be successfully tuned and improved by structural modifications at the chromophores.

Electronic and steric effects on the photo-induced C → E ring-opening of structurally modified furylfulgides

The ultrafast C→E ring-opening reactions of four selectively modified furylfulgides have been studied by means of ultrafast broadband transient absorption spectroscopy after femtosecond laser excitation at λ = 500 nm. A large difference in the dynamics was found in the case of benzannulation at the furyl moiety as an example for an electronic effect by extension of the conjugated π-electron system compared to furylfulgides carrying sterically different alkyl substituents at the central cyclohexadiene (CHD) ring. The measured very similar spectro-temporal absorption maps for the furylfulgides with a methyl or isopropyl group at the CHD ring or an intramolecular alkyl bridge from the CHD to the furyl moiety showed two distinctive excited-state absorptions with slightly different decay times. The first time constant (τ(1) = 0.39-0.57 ps) was assigned to the rapid departure of the excited wavepacket from the Franck-Condon region. The slightly longer second decay time of τ(2) = 0.66-0.92 ps, depending on the compound, was attributed to the electronic deactivation and ring-opening through a conical intersection to the S(0) state. In contrast, the benzannulation at the furyl moiety was found to lead to a bi-phasic excited-state decay with τ(2) = 4.7 ps and a much slower additional contribution of τ(3) = 17.4 ps, ≈25 times longer compared to the normal furylfulgides. The drastic change is attributed to a trapping of excited molecules in a local potential energy minimum en route to the conical intersection.

Ultrafast Photoswitching Dynamics of Azobenzenes with Intra- and Intermolecular Constraints

Femtosecond time-resolved absorption and emission spectroscopy has been used to study the ultrafast photoinduced processes of azobenzenes (ABs) influenced by intra- and intermolecular constraints. For diazocine, an AB with an intramolecular bridge, accelerated molecular dynamics and increased switching efficiencies demonstrate that favourable pre-orientation and restricted molecular degrees of freedom in rigidified molecules may lead to improved optical switching properties. The significant effects of push–pull substitution were studied for the prototypical AB derivative Disperse Red 1 (DR1), which was shown to undergo sequential electronic deactivation and isomerisation. Finally, dramatic increases of the excited-state lifetimes of AB switches covalently embedded into polymeric micronetworks indicate that the photoisomerisation is severely resisted by mechanical forces inside the polymer environment. AB-functionalised polymer materials should thus avoid cross-linking or entanglement of the chromophores and provide ample free volume. Overall, the results demonstrate that detailed insight into the ultrafast photoswitching dynamics can provide guidelines for the design of photoswitchable systems with better performance.