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Novel dyes were prepared by simple “click CuAAC” attachment of a triarylborane–alkyne to the azide side chain of an amino acid yielding triarylborane dye 1 which was conjugated with pyrene (dye 2) forming a triarylborane–pyrene FRET pair. In contrast to previous cationic triarylboranes, the novel neutral dyes interact only with proteins, while their affinity to DNA/RNA is completely abolished. Both the reference triarylborane amino acid and triarylborane–pyrene conjugate bind to BSA and the hDPP III enzyme with high affinities, exhibiting a strong (up to 100-fold) fluorescence increase, whereby the triarylborane–pyrene conjugate additionally retained FRET upon binding to the protein. Furthermore, the triarylborane dyes, upon binding to the hDPP III enzyme, did not impair its enzymatic activity under a wide range of experimental conditions, thus being the first non-covalent fluorimetric markers for hDPP III, also applicable during enzymatic reactions with hDPP III substrates.
Blending different low molecular weight gelators (LMWGs) provides a convenient route to tune the properties of a gel and incorporate functionalities such as fluorescence. Blending a series of gelators having a common bis-urea motif, and functionalised with different amino acid-derived end-groups and differing length alkylene spacers is reported. Fluorescent gelators incorporating 1- and 2-pyrenyl moieties provide a probe of the mixed systems alongside structural and morphological data from powder diffraction and electron microscopy. Characterisation of the individual gelators reveals that although the expected α-urea tape motif is preserved, there is considerable variation in the gelation properties, molecular packing, fibre morphology and rheological behaviour. Mixing of the gelators revealed examples in which: 1) the gels formed separate, orthogonal networks maintaining their own packing and morphology, 2) the gels blended together into a single network, either adopting the packing and morphology of one gelator, or 3) a new structure not seen for either of the gelators individually was created. The strong binding of the urea functionalities to anions was exploited as a means of breaking down the gel structure, and the use of fluorescent gel blends provides new insights into anion-mediated gel dissolution.
The synthesis and characterization of laterally extended azabora[5]‐, ‐[6]‐ and ‐[7]helicenes, assembled from N‐heteroaromatic and dibenzo[g,p]chrysene building blocks is described. Formally, the π‐conjugated systems of the pristine azaborole helicenes were enlarged with a phenanthrene unit leading to compounds with large Stokes shifts, significantly enhanced luminescence quantum yields (Φ) and dissymmetry factors (g\(_{lum}\)). The beneficial effect on optical properties was also observed for helical elongation. The combined contributions of lateral and helical extensions resulted in a compound showing green emission with Φ of 0.31 and |g\(_{lum}\)| of 2.2×10\(^{−3}\), highest within the series of π‐extended azaborahelicenes and superior to emission intensity and chiroptical response of its non‐extended congener. This study shows that helical and lateral extensions of π‐conjugated systems are viable strategies to improve features of azaborole helicenes. In addition, single crystal X‐ray analysis of configurationally stable [6]‐ and ‐[7]helicenes was used to provide insight into their packing arrangements.
Two types of helically chiral compounds bearing one and two boron atoms were synthesized by a modular approach. Formation of the helical scaffolds was executed by the introduction of boron to flexible biaryl and triaryl derived from small achiral building blocks. All‐ortho‐fused azabora[7]helicenes feature exceptional configurational stability, blue or green fluorescence with quantum yields (Φ\(_{fl}\)) of 18–24 % in solution, green or yellow solid‐state emission (Φ\(_{fl}\) up to 23 %), and strong chiroptical response with large dissymmetry factors of up to 1.12×10\(^{-2}\). Azabora[9]helicenes consisting of angularly and linearly fused rings are blue emitters exhibiting Φ\(_{fl}\) of up to 47 % in CH\(_{2}\)Cl\(_{2}\) and 25 % in the solid state. As revealed by the DFT calculations, their P–M interconversion pathway is more complex than that of H1. Single‐crystal X‐ray analysis shows clear differences in the packing arrangement of methyl and phenyl derivatives. These molecules are proposed as primary structures of extended helices.
Efficient quadrupolar chromophores (A–pi–A) with triarylborane moieties as acceptors have been studied by the Marder group regarding their non‐linear optical properties and two‐photon absorption ability for many years. Within the present work, this class of dyes found applications in live‐cell imaging. Therefore, the dyes need to be water‐soluble and water‐stable in diluted aqueous solutions, which was examined in Chapter 2. Furthermore, the influence of the pi‐bridge on absorption and emission maxima, fluorescence quantum yields and especially the two-photon absorption properties of the chromophores was investigated in Chapter 3. In Chapter 4, a different strategy for the design of efficient two‐photon excited fluorescence imaging dyes was explored using dipoles (D–A) and octupoles (DA3). Finding the optimum balance between water‐stability and pi‐conjugation and, therefore, red‐shifted absorption and emission and high fluorescence quantum yields, was investigated in Chapter 5
Two different chromophores, namely a dipolar and an octupolar system, were prepared and their linear and nonlinear optical properties as well as their bioimaging capabilities were compared. Both contain triphenylamine as the donor and a triarylborane as the acceptor, the latter modified with cationic trimethylammonio groups to provide solubility in aqueous media. The octupolar system exhibits a much higher two‐photon brightness, and also better cell viability and enhanced selectivity for lysosomes compared with the dipolar chromophore. Furthermore, both dyes were applied in two‐photon excited fluorescence (TPEF) live‐cell imaging.
Up to three polychlorinated pyridyldiphenylmethyl radicals bridged by a triphenylamine carrying electron withdrawing (CN), neutral (Me), or donating (OMe) groups were synthesized and analogous radicals bridged by tris(2,6‐dimethylphenyl)borane were prepared for comparison. All compounds were as stable as common closed‐shell organic compounds and showed significant fluorescence upon excitation. Electronic, magnetic, absorption, and emission properties were examined in detail, and experimental results were interpreted using DFT calculations. Oxidation potentials, absorption and emission energies could be tuned depending on the electron density of the bridges. The triphenylamine bridges mediated intramolecular weak antiferromagnetic interactions between the radical spins, and the energy difference between the high spin and low spin states was determined by temperature dependent ESR spectroscopy and DFT calculations. The fluorescent properties of all radicals were examined in detail and revealed no difference for high and low spin states which facilitates application of these dyes in two‐photon absorption spectroscopy and OLED devices.
The 2- and 2,7- substituted para-N-methylpyridinium pyrene cations show high-affinity intercalation into ds-DNAs, whereas their non-methylated analogues interacted with ds-DNA/RNA only in the protonated form (at pH 5), but not at physiological conditions (pH 7). The fluorescence from non-methylated analogues was strongly dependent on the protonation of the pyridines; consequently, they act as fluorescence ratiometric probes for simultaneous detection of both ds-DNA and BSA at pH 5, relying on the ratio between intensities at 420 nm (BSA specific) and 520 nm (DNA specific), whereby exclusively ds-DNA sensing could be switched-off by adjustment to pH 7. Only methylated, permanently charged pyrenes show photoinduced cleavage of circular DNA, attributed to pyrene-mediated irradiation-induced production of singlet oxygen. Consequently, the moderate toxicity of these cations against human cell lines is strongly increased upon irradiation. Detailed studies revealed increased total ROS production in cells treated by the compounds studied, accompanied by cell swelling and augmentation of cellular complexity. The most photo-active 2-para-N-methylpyridinium pyrene showed significant localization at mitochondria, its photo-bioactivity likely due to mitochondrial DNA damage. Other derivatives were mostly non-selectively distributed between various cytoplasmic organelles, thus being less photoactive.
Three different perfluoroalkylated borafluorenes (\(^{F}\)Bf) were prepared and their electronic and photophysical properties were investigated. The systems have four trifluoromethyl moieties on the borafluorene moiety as well as two trifluoromethyl groups at the ortho positions of their exo‐aryl moieties. They differ with regard to the para substituents on their exo‐aryl moieties, being a proton \(^{F}\)Xyl\(^{F}\)Bf, \(^{F}\)Xyl: 2,6‐bis(trifluoromethyl)phenyl), a trifluoromethyl group (\(^{F}\)Mes\(^{F}\)Bf, \(^{F}\)Mes: 2,4,6‐tris(trifluoromethyl)phenyl) or a dimethylamino group (p‐NMe\(_{2}\)‐\(^{F}\)Xyl\(^{F}\)Bf, p‐NMe\(_{2}\)‐\(^{F}\)Xyl: 4‐(dimethylamino)‐2,6‐bis(trifluoromethyl)phenyl), respectively. All derivatives exhibit extraordinarily low reduction potentials, comparable to those of perylenediimides. The most electron‐deficient derivative \(^{F}\)Mes\(^{F}\)Bf was also chemically reduced and its radical anion isolated and characterized. Furthermore, all compounds exhibit very long fluorescent lifetimes of about 250 ns up to 1.6 μs; however, the underlying mechanisms responsible for this differ. The donor‐substituted derivative p‐NMe\(_{2}\)‐\(^{F}\)Xyl\(^{F}\)Bf exhibits thermally activated delayed fluorescence (TADF) from a charge‐transfer (CT) state, whereas the \(^{F}\)Mes\(^{F}\)Bf and FXylFBf borafluorenes exhibit only weakly allowed locally excited (LE) transitions due to their symmetry and low transition‐dipole moments.
Bisdiynes undergo Pd(0)-catalyzed cyclization, forming azulene and naphthalene products. When dibenzylideneacetone is present in the reaction, it undergoes a [2+2+2] cyclization with the bisdiyne, forming cyclohexadiene derivatives. Ni(0) catalyzes the [2+2+2] cycloaddition of diynes with tolanes towards alkynylated o-terphenyl derivatives. The D-A substituted products are solvatochromic, fluorescent dyes with high quantum yields and short lifetimes. Bis-triarylborane tetrayne dyes were synthesized in both neutral and tetracationic forms, as potential DNA/RNA sensor. Both molecules are weakly fluorescent in solution and exhibit characteristic alkyne absorptions in the Raman spectra. Tributyl phosphine catalyzes the trans-hydroboration of 1,3-butadiynes with HBpin. We confirmed experimentally via NMR and HRMS experiments, that phosphine attack on the diyne is a key step in the catalytic cycle.