Using the long-range corrected (LC) density functional theory (DFT) scheme introduced by Iikura et al. [J. Chem. Phys. 115, 3540 (2001)] and the Coulomb-attenuating model (CAM-B3LYP) of Yanai et al. [Chem. Phys. Lett. 393, 51 (2004)], we have calculated the longitudinal dipole moments and static electronic first hyperpolarizabilities of increasingly long polymehtineimine oligomers. For comparison purposes Hartree-Fock (HF), Møller-Plesset perturbation theory (MP2), and conventional pure and hybrid functionals have been considered as well. HF, generalized gradient approximation (GGA), and conventional hybrids provide too large dipole moments for long oligomers, while LC-DFT allows to reduce the discrepancy with respect to MP2 by a factor of 3. For the first hyperpolarizability, the incorrect evolution with the chain length predicted by HF is strongly worsened by BLYP, Perdew-Burke-Ernzerhof (PBE), and also by B3LYP and PBE0. On the reverse, LC-BLYP and LC-PBE hyperpolarizabilities are correctly predicted to be positive (but for the two smallest chains). Indeed, for medium and long oligomers LC hyperpolarizabilities are slightly smaller than MP2 hyperpolarizabilities, as it should be. CAM-B3LYP also strongly improves the B3LYP results, though a bit less impressively for small chain lengths. The present study demonstrates the efficiency of long-range DFT, even in very pathological cases.

Donor–acceptor Stenhouse adducts (DASAs) are negative photochromes that hold great promise for a variety of applications. Key to optimizing their switching properties is a detailed understanding of the photoswitching mechanism, which, as yet, is absent. Here we characterize the actinic step of DASA-photoswitching and its key intermediate, which was studied using a combination of ultrafast visible and IR pump–probe spectroscopies and TD-DFT calculations. Comparison of the time-resolved IR spectra with DFT computations allowed to unambiguously identify the structure of the intermediate, confirming that light absorption induces a sequential reaction path in which a Z–E photoisomerization of C₂–C₃ is followed by a rotation around C₃–C₄ and a subsequent thermal cyclization step. First and second-generation DASAs share a common photoisomerization mechanism in chlorinated solvents with notable differences in kinetics and lifetimes of the excited states. The photogenerated intermediate of the second-generation DASA was photo-accumulated at low temperature and probed with time-resolved spectroscopy, demonstrating the photoreversibility of the isomerization process. Taken together, these results provide a detailed picture of the DASA isomerization pathway on a molecular level.

Light is an exceptional external stimulus for establishing precise control over the properties and functions of chemical and biological systems, which is enabled through the use of molecular photoswitches. Ideal photoswitches are operated with visible light only, show large separation of absorption bands and are functional in various solvents including water, posing an unmet challenge. Here we show a class of fully-visible-light-operated molecular photoswitches, Iminothioindoxyls (ITIs) that meet these requirements. ITIs show a band separation of over 100 nm, isomerize on picosecond time scale and thermally relax on millisecond time scale. Using a combination of advanced spectroscopic and computational techniques, we provide the rationale for the switching behavior of ITIs and the influence of structural modifications and environment, including aqueous solution, on their photochemical properties. This research paves the way for the development of improved photo-controlled systems for a wide variety of applications that require fast responsive functions.

Donor–acceptor Stenhouse adducts (DASAs) are negative photochromes that switch with visible light and are highly promising for applications ranging from smart materials to biological systems. However, the strong solvent dependence of the photoswitching kinetics limits their application. The nature of the photoswitching mechanism in different solvents is key for addressing the solvatochromism of DASAs, but as yet has remained elusive. Here, we employ spectroscopic analyses and TD‐DFT calculations to reveal changing solvatochromic shifts and energies of the species involved in DASA photoswitching. Time‐resolved visible pump‐probe spectroscopy suggests that the primary photochemical step remains the same, irrespective of the polarity and protic nature of the solvent. Disentangling the different factors determining the solvent‐dependence of DASA photoswitching, presented here, is crucial for the rational development of applications in a wide range of different media.

Preparation of graphene derivatives using fluorographene (FG) as a precursor has become a key strategy for the large-scale synthesis of new 2-D materials (e.g. graphene acid, cyanographene, allyl-graphene) with tailored physicochemical properties. However, to gain full control over the derivatization process, it is essential to understand the reaction mechanisms and accompanying processes that affect the composition and structure of the final products. Despite the strength of C–F bonds and high chemical stability of perfluorinated hydrocarbons, FG is surprisingly susceptible to reactions under ambient conditions. There is clear evidence that nucleophilic substitution on FG is accompanied by spontaneous defluorination, and solvent-induced defluorination can occur even in the absence of any nucleophilic agent. Here, we show that distributed radical centers (fluorine vacancies) on the FG surface need to be taken into account in order to rationalize the defluorination mechanism. Depending on the environment, these radical centers can react as electron acceptors, electrophilic sites and/or cause homolytic bond cleavages. We also propose a new radical mechanism of FG defluorination in the presence of N,N′-dimethylformamide (DMF) solvent. Spin-trap experiments as well as ¹⁹F NMR measurements unambiguously confirmed formation of N,N′-dimethylformyl radicals and also showed that N,N′-dimethylcarbamoyl fluoride plays a key role in the proposed mechanism. These findings imply that point defects in 2D materials should be considered as key factor determining their chemical properties and reactivity.