Bromopyrene Symphony: Synthesis and Characterisation of Isomeric Derivatives at Non-K Region and Nodal Positions for Diverse Functionalisation Strategies.

Pyrene, a renowned aromatic hydrocarbon, continues to captivate researchers due to its versatile properties and potential applications across various scientific domains. Among its derivatives, bromopyrenes stand out for their significance in synthetic chemistry, materials science, and environmental studies. The strategic functionalisation of pyrene at non-K region and nodal positions is crucial for expanding its utility, allowing for diverse functionalisation strategies. Bromo-substituted precursors serve as vital intermediates in synthetic routes; however, the substitution pattern of bromoderivatives significantly impacts their subsequent functionalisation and properties, posing challenges in synthesis and purification. Understanding the distinct electronic structure of pyrene is pivotal, dictating the preferential electrophilic aromatic substitution reactions at specific positions. Despite the wealth of literature, contradictions and complexities persist in synthesising suitably substituted bromopyrenes due to the unpredictable nature of substitution reactions. Building upon historical precedents, this study provides a comprehensive overview of bromine introduction in pyrene derivatives, offering optimised synthesis conditions based on laboratory research. Specifically, the synthesis of mono-, di-, tri-, and tetrabromopyrene isomers at non-K positions (1-, 3-, 6-, 8-) and nodal positions (2-, 7-) is systematically explored. By elucidating efficient synthetic methodologies and reaction conditions, this research contributes to advancing the synthesis and functionalisation strategies of pyrene derivatives, unlocking new possibilities for their utilisation in various fields.

The Impact of a 1,2,3-Triazole Motif on the Photophysical Behavior of Non-K Tetrasubstituted Pyrene with a Substitution Pattern Providing the Long Axial Symmetry.

1,3,6,8-Tetrasubstituted pyrene derivatives with two types of substituents (4-(2,2-dimethylpropyloxy)pyridine, 1-decyl-1,2,3-triazole, 1-benzyl-1,2,3-triazole, and pyrazole), substituted in such a way that provides the long axial symmetry, are prepared and characterized in the present study. To the best of our knowledge, the pyrene derivative containing the same heteroaryl motif (triazole) but substituted by two various alkyls, straight decyl and benzyl-based side chains (C), is reported for the first time. For comparison, compounds with one kind of triazole motif and substituted pyridine or pyrazole groups were prepared (A and B). The photophysical properties of all molecules were evaluated by thermogravimetric analysis (TGA) and UV-Vis spectroscopy (absorption and emission spectra, quantum yields, and fluorescence lifetimes). The obtained results were compared to analogues substituted at the 1,3,6,8 positions by one kind of substituent and also with all the 1,3,6,8-tetrasubstituted pyrenes reported in the literature substituted by two kinds of substituents with a substitution pattern that provides long axial symmetry. In addition, theoretical studies based on DFT and TD-DFT were performed that supported the interpretation of the experimental results. The photophysical properties of tetrasubstituted pyrene derivatives having triazole units at the 1,8-positions, respectively, and other identical substituents at the 3,6 positions show the dominance of triazole units in the pyrene framework; the dominance is even higher in the case of the substitution of 1,3,6,8 positions by triazoles, but containing two various alkyls.

DFT/TD-DFT Framework of Mixed-Metal Complexes with Symmetrical and Unsymmetrical Bridging Ligands-Step-By-Step Investigations: Mononuclear, Dinuclear Homometallic, and Heterometallic for Optoelectronic Applications.

Recently, mono- and dinuclear complexes have been in the interest of scientists due to their potential application in optoelectronics. Herein, progressive theoretical investigations starting from mononuclear followed by homo- and heterometallic dinuclear osmium and/or ruthenium complexes with NCN-cyclometalating bridging ligands substituted by one or two kinds of heteroaryl groups (pyrazol-1-yl and 4-(2,2-dimethylpropyloxy)pyrid-2-yl) providing the short/long axial symmetry or asymmetry are presented. Step-by-step information about the particular part that built the mixed-metal complexes is crucial to understanding their behavior and checking the necessity of their eventual studies. Evaluation by using density functional theory (DFT) calculations allowed gaining information about the frontier orbitals, energy gaps, and physical parameters of complexes and their oxidized forms. Through time-dependent density functional theory (TD-DFT), calculations showed the optical properties, with a particular emphasis on the nature of low-energy bands. The presented results are a clear indication for other scientists in the field of chemistry and materials science.

New derivatives of 4'-phenyl-2,2':6',2″-terpyridine as promising anticancer agents.

Terpyridine derivatives are known from their broad application including anticancer properties. In this work we present the newly synthesized 4'-phenyl-2,2':6',2″-terpyridine group with high antiproliferative activity. We suggest that these compounds influence cellular redox homeostasis. Cancer cells are particularly susceptible to any changes in the redox balance because of their handicapped and inefficient antioxidant cellular systems. The antiproliferative activity of the studied compounds was tested on five different cell lines that represent several types of tumours; glioblastoma, leukemia, breast, pancreatic and colon. Additionally, we also tested their selectivity towards normal cells. We performed molecular biology studies in order to detect the response of a cell to its treatment with the compounds that were tested. We looked at the in-depth changes in the proteins and cellular pathways that lead to cell cycle inhibition (G0/G1 and S), and consequently, death on the apoptosis and autophagy pathways. We proved that the studied compounds targeted DNA as well. Special attention was paid to the targets connected with ROS generation.

Investigations of New Phenothiazine-Based Compounds for Dye-Sensitized Solar Cells with Theoretical Insight.

New D-π-D-π-A low-molecular-weight compounds, based on a phenothiazine scaffold linked via an acetylene unit with various donor moiety and cyanoacrylic acid anchoring groups, respectively, were successfully synthesized. The prepared phenothiazine dyes were entirely characterized using nuclear magnetic resonance (NMR) spectroscopy and elemental analysis. The compounds were designed to study the relationship between end-capping donor groups' structure on their optoelectronic and thermal properties as well as the dye-sensitized solar cells' performance. The effect of π-conjugation enlargement by incorporation of different heterocyclic substituents possessing various electron-donor affinities was systematically experimentally and theoretically examined. Density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations were implemented to determine the electronic properties of the novel molecules.

Anticancer activity of 4'-phenyl-2,2':6',2″-terpyridines - behind the metal complexation.

Terpyridine complexes are known for their broad biological activities, of which their anticancer potency is the most extensively studied. Strikingly, free ligand activity has rarely been described in the literature. In this study, a lipophilic derivative of terpyridine 4'-(1-decyl-2,3-triazol-4-yl)phenyl-2,2':6',2″-terpyridine (L) and its complexes were investigated to determine their mechanism of anticancer activity. Our results show that a free ligand expresses the same level of activity on a panel of cancer cells with a low toxicity towards normal fibroblasts as complexes with Cd, Zn or Cu. Breast cancer (MCF-7 cell line) was the most vulnerable for the tested compounds with the IC50 values in the nanomolar range (IC50 = 40 nM for L.) The addition of Cu(II) ions increased its activity even further, thus suggesting that ligand exchange and ROS production are the main components of its activity. A cell cycle analysis indicated its inhibition at the G0/G1 phase and the subsequent apoptosis as the cell death mode. A detailed analysis of the protein level that was involved in the aforementioned processes confirmed previous results. Furthermore, the reactive oxygen species generation and DNA intercalation confirmed its cleaving activity.

Non-K Region Disubstituted Pyrenes (1,3-, 1,6- and 1,8-) by (Hetero)Aryl Groups-Review.

Disubstituted pyrenes at the non-K region by the same or different (hetero)aryl groups have proven to be an increasingly interesting area of research for scientists over the last decade due to their optical and photophysical properties. However, in this area, there is no systematization of the structures and synthesis methods nor their limitations. In this review, all approaches to the synthesis of these compounds, starting from the commercially available pyrene are described. Herein, the ways of obtaining of disubstituted intermediates based on bromination and acylation reaction are presented. This is crucial in the determination of the possibility of further functionalization by using coupling, cycloaddition, condensation, etc. reactions. Moreover, the application of disubstituted pyrenes in the synthesis of 1,3,6,8-tetrasubstituted was also reviewed. This review describes the directions of research on chemistry of disubstituted pyrenes.

Influence of the substituent D/A at the 1,2,3-triazole ring on novel terpyridine derivatives: synthesis and properties.

In this study, we newly designed and developed a synthesis route based on the 1,3-dipolar cycloaddition of the derivatives of 4'-(1,2,3-triazol-4-yl)phenyl-2,2':6',2''-terpyridine with various (hetero)aryl substituents, differing in electronic character, on a triazol ring. The obtained compounds were comprehensively characterized by UV-Vis spectroscopy and electrochemical and thermal studies. Moreover, preliminary biological tests were conducted. The investigation allowed the selection of materials with the most promising properties with particular emphasis on the nature of the substituents. In addition, theoretical studies (DFT and TD-DFT) were performed to verify the comprehensive understanding of experimental results.

Pyrene derivatives with two types of substituents at positions 1, 3, 6, and 8 - fad or necessity?

1,3,6,8-Tetrasubstituted pyrene derivatives with two types of substituents in an asymmetry or axial symmetry pattern have been prepared and characterized. To the best of our knowledge, these compounds are compared for the first time to their analogs containing the same substituent at all four positions, which explains the need for their synthesis. We present information on the chemistry of pyrenes, which are substituted in the non-K region, to help obtain the most efficient materials. Moreover, theoretical studies were extended to analogs which contain the first type of substituent at positions 1 and 3, whereas the second type of substituent is located at positions 6 and 8, for which the synthesis is nontrivial. The obtained data show which trend these kinds of molecules will follow.

NCN-Coordinating Ligands based on Pyrene Structure with Potential Application in Organic Electronics.

Five novel derivatives of pyrene, substituted at positions 1,3,6,8 with 4-(2,2-dimethylpropyloxy)pyridine (P1), 4-decyloxypyridine (P2), 4-pentylpyridine (P3), 1-decyl-1,2,3-triazole (P4), and 1-benzyl-1,2,3-triazole (P5), are obtained through a Suzuki-Miyaura cross-coupling reaction or CuI -catalyzed 1,3-dipolar cycloaddition reaction, respectively, and characterized thoroughly. TGA measurements reveal the high thermal stability of the compounds. Pyrene derivatives P1-P5 all show photoluminescence (PL) quantum yields (Φ) of approximately 75 % in solution. Solid-state photo- and electroluminescence characteristics of selected compounds as organic light-emitting diodes are tested. In the guest-host configuration, two matrixes, that is, poly(N-vinylcarbazole) (PVK) and a binary matrix consisting of PVK and 2-tert-butylphenyl-5-biphenyl-1,3,4-oxadiazole (PBD) (50:50 wt %), are applied. The diodes show red, green, or blue electroluminescence, depending on both the compound chemical structure and the actual device architecture. In addition, theoretical studies (DFT and TD-DFT) provide a deeper understanding of the experimental results.