Synthesis of Fluorescent C-C Bonded Triazole-Purine Conjugates.

A design toward C-C bonded 2,6-bis(1H-1,2,3-triazol-4-yl)-9H-purine and 2-piperidinyl-6-(1H-1,2,3-triazol-4-yl)-9H-purine derivatives was established using the combination of Mitsunobu, Sonogashira, copper (I) catalyzed azide-alkyne cycloaddition, and SNAr reactions. 11 examples of 2,6-bistriazolylpurine and 14 examples of 2-piperidinyl-6-triazolylpurine intermediates were obtained, in 38-86% and 41-89% yields, respectively. Obtained triazole-purine conjugates expressed good fluorescent properties which were studied in the solution and in the thin layer film for the first time. Quantum yields reached up to 49% in DMSO for bistriazolylpurines and up to 81% in DCM and up to 95% in DMSO for monotriazolylpurines. Performed biological studies in mouse embryo fibroblast, human keratinocyte, and transgenic adenocarcinoma of the mouse prostate cell lines showed that most of obtained triazole-purine conjugates are not cytotoxic. The 50% cytotoxic concentration of the tested derivatives was in the range from 59.6 to 1528.7 µM.

TICT compounds by design: comparison of two naphthalimide-π-dimethylaniline conjugates of different lengths and ground state geometries.

Two new twisted intramolecular charge transfer (TICT) donor-π-acceptor compounds were designed by combining a well-known electron acceptor naphthalimide unit with a classic electron donor dimethylaniline through two types of different rigid linkers. The combined steady-state and time-resolved spectroscopy of molecules in solvents of different polarities in comparison to solid-state solvation experiments of doped polymer matrixes of different polarities allowed distinguishing between solvation and conformation determined processes. The photophysical measurements revealed that non-polar solutions possess high fluorescence quantum yields of up to 70% which is a property of pre-twisted/planar molecules in the excited charge transfer (CT) states. The increase of polarity allows tuning the Stokes shift through all the visible wavelength range up to 8601 cm-1 which is accompanied by a three orders of magnitude drop of fluorescence quantum yields. This is a result of the emerged TICT states as dimethylaniline twists to a perpendicular position against the naphthalimide core. The TICT reaction of molecules enables an additional non-radiative excitation decay channel, which is not present if the twisting is forbidden in a rigid polymer matrix. Transient absorption spectroscopy was employed to visualize the excited state dynamics and to obtain the excited state reaction constants, revealing that TICT may occur from both the Franck-Condon region and the solvated pre-twisted/planar CT states. Both molecules undergo the same photophysical processes, however, a longer linker and thus a higher excited state dipole moment determines the faster excited state reactions.

Diboraanthracene-Doped Polymer Systems for Colour-Tuneable Room-Temperature Organic Afterglow.

Organic ultralong room temperature phosphorescence (RTP), or organic afterglow, is a unique phenomenon, gaining widespread attention due to its far-reaching application potential and fundamental interest. Here, two laterally expanded 9,10-dimesityl-dihydro-9,10-diboraanthracene (DBA) derivatives are demonstrated as excellent afterglow materials for red and blue-green light emission, which is traced back to persistent thermally activated delayed fluorescence and RTP. The lateral substitution of polycyclic DBA scaffold, together with weak transversal electron-donating mesityl groups, ensures the optimal molecular properties for (reverse) intersystem crossing and long-lived triplet states in a rigid poly(methyl methacrylate) matrix. The achieved afterglow emission quantum yields of up to 3 % and 15 %, afterglow lifetimes up to 0.8 s and 3.2 s and afterglow durations up to 5 s and 25 s (for red and blue-green emitters, respectively) are attributed to the properties of single molecules.

Mechanistic Insights into the Photoisomerization of N,N'-Disubstituted Indigos.

N,N'-disubstituted indigos are photoswitchable molecules that have recently caught the attention due to their addressability by red-light. When alkyl and aryl groups are utilized as the N-substituents, the thermal half-lives of Z isomers can be tuned independently while maintaining the advantageous red-shifted absorption spectra. To utilize these molecules in real-world applications, it is of immense importance to understand how their molecular structures as well as the environment influence their switching properties. To this end, we probed their photoisomerization mechanism by carrying out photophysical and computational studies in solvents of different polarities. The fluorescence and transient absorption experiments suggest for more polar excited and transition states, which explains the bathochromic shifts of absorption spectra and shorter thermal half-lives. On the other hand, the quantum chemical calculations reveal that in contrast to N-carbonyl groups, N-alkyl and N-aryl substituents are not strongly conjugated with the indigo chromophore and can thus serve as a tool for tuning the thermal stability of Z isomers. Both approaches are combined to provide in-depth understandings of how indigos undergo photoswitching as well as how they are influenced by N-substituent and the chemical surroundings. These mechanistic insights will serve as guiding principles for designing molecules eyeing broader applications.

Proof of principle of a purine D-A-D' ligand based ratiometric chemical sensor harnessing complexation induced intermolecular PET.

A comprehensive photophysical study of a series of purines, doubly decorated at C2 and C6 positions with identical fragments ranging from electron acceptor to donor groups of different strengths, is presented. The asymmetry of substitutions creates a unique molecular D-A-D' structure possessing two independent electronic charge transfer (CT) systems attributed to each fragment and exhibiting dual-band fluorescence. Moreover, the inherent property of coordination of metal ions by purines was enriched due to a presence of nearby triazoles used as spacers for donor or acceptor fragments. New molecules present a bidentate coordination mode, which makes the assembly of several ligands with one metal cation possible. This property was exploited to create a new concept of a ratiometric chemical fluorescence sensor involving the photoinduced electron transfer between branches of different ligands as a mechanism of fluorescence modulation.