Parent, unsubstituted porphycene and its two derivatives: 2,7,12,17-tetra-n-propylporphycene and 2,7,12,17-tetra-t-butylporphycene were substituted at the meso position with amino and nitro groups. These two families of porphycenes were characterized in detail with respect to their spectral, photophysical, and tautomeric properties. Two trans tautomers of similar energies coexist in the ground electronic state, but only one form dominates in the lowest excited singlet state. Absorption, magnetic circular dichroism (MCD), and emission anisotropy combined with quantum-chemical calculations led to the assignment of S1 and S2 transitions in both tautomers. Compared with the parent porphycene, the S1–S2 energy gap significantly increases; for one tautomeric form, the effect is twice as large as for the other. Both amino- and nitroporphycenes emit single fluorescence; previously reported dual emission of aminoporphycenes is attributed to a degradation product. Introduction of bulky t-butyl groups leads to a huge decrease in fluorescence intensity; this effect, arising from the interaction of the meso substituent with the adjacent t-butyl moiety, is particularly strong in the nitro derivative.

The excited-state properties of an amphiphilic porphyrin-fullerene dyad and of its porphyrin analogue adsorbed at the dodecane/water interface are investigated by using surface second-harmonic generation. Although the porphyrin is formally centrosymmetric, the second-harmonic spectra of both compounds are dominated by the intense Soret band of the porphyrin. Polarization-selective measurements and molecular dynamics simulations suggest an angle of about 45° between the donor-acceptor axis and the interfacial plane, with the porphyrin interacting mostly with the nonpolar phase. Time-resolved measurements reveal a marked concentration dependence of the dynamics of both compounds upon Q-band excitation, indicating the occurrence of intermolecular quenching processes. The significant differences in dynamics and spectra between the dyad and the porphyrin analogue are explained by a self-quenching of the excited dyad via an intermolecular electron transfer.

Understanding structure–property relationships in multichromophoric molecular architectures is a crucial step in establishing new design principles in organic electronics as well as to fully understand how nature exploits solar energy. Here, we study the excited state dynamics of three bichromophores consisting of two perylene chromophores linked to three different crown-ether backbones, using stationary and ultrafast electronic spectroscopy combined with molecular dynamics simulations. The conformational space available to the bichromophores depends on the structure and geometry of the crown-ether and can be significantly changed upon cation binding, strongly affecting the excited-state dynamics. We show that, depending on the conformational restrictions and the local environment, the nature of the excited state varies greatly, going from an excimer to a symmetry-broken charge separated state. These results can be rationalised in terms of a structure–property relationship that includes the effect of the local environment.

A thorough understanding of the microscopic mechanism of excited-state proton transfer (ESPT) and the influence of the solvent environment on its dynamics are of great fundamental interest. We present here a detailed investigation of an ESPT to solvent (DMSO) using time-resolved broadband fluorescence and transient absorption spectroscopies. All excited-state species are resolved spectrally and kinetically using a global target analysis based on the two-step Eigen-Weller model. Reversibility of the initial short-range proton transfer producing excited contact ion pairs (CIP*) is observed unambiguously in fluorescence and must be explicitly considered to obtain the individual rate constants. Close inspection of the early dynamics suggests that the relative populations of the protonated form (ROH*) and CIP* are governed by solvent relaxation that influences the relative energies of the excited states. This constitutes a breakdown of the Eigen-Weller model, although the overall agreement between the data and the analysis using classical rate equations is excellent.

Polar solvation dynamics of six 7-aminocoumarins and 4-aminophthalimide (4AP) are investi- gated using broadband FLuorescence UP–conversion Spectroscopy (FLUPS) combined with a global analysis based on time-dependent band-shape functions. The solvation dynamics of the coumarins in ethanol exhibit only minor differences but are, however, significantly different from that of 4AP. The band-shape parameters, width and asymmetry, exhibit much larger variation even among the coumarins and are correlated with the amount of excess excitation energy. Differences in the solvation dynamics of 4AP and a selected coumarin, C151, are also observed in dimethyl sulfoxide demonstrating the molecularity of solvation i.e. solvation depends on the solute and does not solely reflect the dynamic properties of the solvent. These differences are attributed to specific solute-solvent interactions due to hydrogen bonding. In a weakly interacting solvent, benzonitrile, the solvation dynamics of 4AP and C151 are nearly identical.

Ultrafast photochemical reactions in liquids occur on similar or shorter time scales compared to the equilibration of the optically populated excited state. This equilibration involves the relaxation of intramolecular and/or solvent modes. As a consequence, the reaction dynamics are no longer exponential, cannot be quantified by rate constants, and may depend on the excitation wavelength contrary to slower photochemical processes occurring from equilibrated excited states. Such ultrafast photoinduced reactions do no longer obey the Kasha–Vavilov rule. Nonequilibrium effects are also observed in diffusion-controlled intermolecular processes directly after photoexcitation, and their proper description gives access to the intrinsic reaction dynamics that are normally hidden by diffusion. Here we discuss these topics in relation to ultrafast organic photochemical reactions in homogeneous liquids. Discussed reactions include intra- and intermolecular electron- and proton-transfer processes, as well as photochromic reactions occurring with and without bond breaking or bond formation, namely ring-opening reactions and cis–trans isomerizations, respectively.