Selenous Acid in an Aromatic Framework: Insights Into a Temperature-Sensitive Internal Redox System from the Solid State

Straub, Laura; Wickleder, Ma­thias S.; Rasche, Bertold

doi:10.1021/acs.inorgchem.1c03734

Cited by 1 publication

(1 citation statement)

References 30 publications

(44 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…From 3 , it is possible to oxidize the methyl groups with selenium dioxide in refluxing dioxane to produce bisaldehyde 4,7-diformylphen 799 , similarly to the oxidation of neocuproine to form 565 . Different yields have been reported from 43% to 96%. ,,− Then oxidation of the formyl group into carboxylic acid has been performed using nitric acid, leading to the 4,7-dicarboxylic acid phen 800 with 33%, 62%, or 43% yield (Scheme ).…”

Section: Divergent Synthesis Pathwaysmentioning

confidence: 99%

Fifty Shades of Phenanthroline: Synthesis Strategies to Functionalize 1,10-Phenanthroline in All Positions

Queffélec,

Pati,

Pellegrin

2024

Chem. Rev.

View full text Add to dashboard Cite

1,10-Phenanthroline (phen) is one of the most popular ligands ever used in coordination chemistry due to its strong affinity for a wide range of metals with various oxidation states. Its polyaromatic structure provides robustness and rigidity, leading to intriguing features in numerous fields (luminescent coordination scaffolds, catalysis, supramolecular chemistry, sensors, theranostics, etc.). Importantly, phen offers eight distinct positions for functional groups to be attached, showcasing remarkable versatility for such a simple ligand. As a result, phen has become a landmark molecule for coordination chemists, serving as a must-use ligand and a versatile platform for designing polyfunctional arrays. The extensive use of substituted phenanthroline ligands with different metal ions has resulted in a diverse array of complexes tailored for numerous applications. For instance, these complexes have been utilized as sensitizers in dye-sensitized solar cells, as luminescent probes modified with antibodies for biomaterials, and in the creation of elegant supramolecular architectures like rotaxanes and catenanes, exemplified by Sauvage’s Nobel Prize-winning work in 2016. In summary, phen has found applications in almost every facet of chemistry. An intriguing aspect of phen is the specific reactivity of each pair of carbon atoms ([2,9], [3,8], [4,7], and [5,6]), enabling the functionalization of each pair with different groups and leading to polyfunctional arrays. Furthermore, it is possible to differentiate each position in these pairs, resulting in non-symmetrical systems with tremendous versatility. In this Review, the authors aim to compile and categorize existing synthetic strategies for the stepwise polyfunctionalization of phen in various positions. This comprehensive toolbox will aid coordination chemists in designing virtually any polyfunctional ligand. The survey will encompass seminal work from the 1950s to the present day. The scope of the Review will be limited to 1,10-phenanthroline, excluding ligands with more intracyclic heteroatoms or fused aromatic cycles. Overall, the primary goal of this Review is to highlight both old and recent synthetic strategies that find applicability in the mentioned applications. By doing so, the authors hope to establish a first reference for phenanthroline synthesis, covering all possible positions on the backbone, and hope to inspire all concerned chemists to devise new strategies that have not yet been explored.

show abstract