ABSTRACT
Indane-1,3-dione is a versatile building block used in numerous applications ranging from biosensing, bioactivity, bioimaging to electronics or photopolymerization. In this review, an overview of the different chemical reactions enabling access to this scaffold but also to the most common derivatives of indane-1,3-dione are presented. Parallel to this, the different applications in which indane-1,3-dione-based structures have been used are also presented, evidencing the versatility of this structure.
Subject(s)
Indans , Indans/chemistryABSTRACT
We use an on-surface synthesis approach to drive the homocoupling reaction of a simple dithiophenyl-functionalized precursor on Cu(111). The C-S activation reaction is initiated at low annealing temperature and yields unsaturated hydrocarbon chains interconnected in a fully conjugated reticulated network. High-resolution atomic force microscopy imaging reveals the opening of the thiophenyl rings and the presence of trans- and cis-oligoacetylene chains as well as pentalene units. The chemical transformations were studied by C 1s and S 2p core level photoemission spectroscopy and supported by theoretical calculations. At higher annealing temperature, additional cyclization reactions take place, leading to the formation of small graphene flakes.
ABSTRACT
In this article, different substituents (benzoyl, acetyl, styryl) are introduced onto the carbazole scaffold to obtain 8 novel carbazole derivatives. Interestingly, a benzoyl substituent, connected to a carbazole group, could form a benzophenone moiety, which composes a monocomponent Type II benzophenone-carbazole photoinitiator (PI). The synergetic effect of the benzophenone moiety and the amine in the carbazole moiety is expected to produce high performance photoinitiating systems (PISs) for the free radical photopolymerization (FRP). For different substituents, clear effects on the light absorption properties are demonstrated using UV-Visible absorption spectroscopy. Benzophenone-carbazole PIs can initiate the FRP of acrylates alone (monocomponent Type II photoinitiator behavior). In addition, fast polymerization rates and high function conversions of acrylate are observed when an amine and/or an iodonium salt are added in systems. Benzophenone-carbazole PIs have good efficiencies in cationic photopolymerization (CP) upon LED @ 365 nm irradiation in the presence of iodonium salt. In contrast, other PIs without synergetic effect demonstrate unsatisfied photopolymerization profiles in the same conditions. The best PIS identified for the free radical photopolymerization were used in three-dimensional (3D) printing. Steady state photolysis and fluorescence quenching experiments were carried out to investigate the reactivity and the photochemistry and photophysical properties of PIs. The free radicals, generated from the studied PISs, are detected by the electron spin resonance - spin trapping technique. The proposed chemical mechanisms are provided and the structure/reactivity/efficiency relationships are also discussed. All the results showed that the benzophenone-carbazole PIs have a good application potential, and this work provides a rational design route for PI molecules. Remarkably, BPC2-BPC4, C6, C8 were never synthetized before; therefore, 5 of the 8 compounds are completely new.
ABSTRACT
A series of ten push-pull chromophores comprising 1H-cyclopenta[b]naphthalene-1,3(2H)-dione as the electron-withdrawing group have been designed, synthesized, and characterized by UV-visible absorption and fluorescence spectroscopy, cyclic voltammetry and theoretical calculations. The solvatochromic behavior of the different dyes has been examined in 23 solvents and a positive solvatochromism has been found for all dyes using the Kamlet-Taft solvatochromic relationship, demonstrating the polar form to be stabilized in polar solvents. To establish the interest of this polyaromatic electron acceptor only synthesizable in a multistep procedure, a comparison with the analog series based on the benchmark indane-1,3-dione (1H-indene-1,3(2H)-dione) has been done. A significant red-shift of the intramolecular charge transfer band has been found for all dyes, at a comparable electron-donating group. Parallel to the examination of the photophysical properties of the different chromophores, a major improvement of the synthetic procedure giving access to 1H-cyclopenta[b]naphthalene-1,3(2H)-dione has been achieved.
ABSTRACT
The fabrication of macromolecular organic structures on surfaces is one major concern in materials science. Nanoribbons, linear polymers, and porous nanostructures have gained a lot of interest due to their possible applications ranging from nanotemplates, catalysis, optoelectronics, sensors, or data storage. During decades, supramolecular chemistry has constituted an unavoidable approach for the design of well-organized structures on surfaces displaying a long-range order. Following these initial works, an important milestone has been established with the formation of covalent bonds between molecules. Resulting from this unprecedented approach, various nanostructures of improved thermal and chemical stability compared to those obtained by supramolecular chemistry and displaying unique and unprecedented properties have been developed. However, a major challenge exists: the growth control is very delicate and a thorough understanding of the complex mechanisms governing the on-surface chemistry is still needed. Recently, a new approach consisting in elaborating macromolecular structures by combining consecutive steps has been identified as a promising strategy to elaborate organic structures on surface. By designing precursors with a preprogrammed sequence of reactivity, a hierarchical or a sequential growth of 1D and 2D structures can be realized. In this review, the different reaction combinations used for the design of 1D and 2D structures are reported. To date, eight different sequences of reactions have been examined since 2008, evidencing the intense research activity existing in this field.
