From Stimuli-Responsive Polymorphic Organic Dye Crystals to Photoluminescent Cationic Open-Framework Metal Phosphate

Four photoluminescent dye crystals, TPB-n (n = 1–3) and TPCH, have been synthesized in isolation from carbon–carbon coupling of 4,4′-trimethylene-dipyridine (tmdp) in the absence of organic solvent and catalyst via in situ one-pot metal/ligand oxidative-dehydrogenation reactions. Large crystals have...

Ausführliche Beschreibung

Gespeichert in:
Bibliographische Detailangaben
Veröffentlicht in:Journal of the American Chemical Society 2012-06, Vol.134 (24), p.9848-9851
Hauptverfasser: Chang, Yu-Chuan, Wang, Sue-Lein
Format: Artikel
Sprache:eng
Online-Zugang:Volltext
Tags: Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
Beschreibung
Zusammenfassung:Four photoluminescent dye crystals, TPB-n (n = 1–3) and TPCH, have been synthesized in isolation from carbon–carbon coupling of 4,4′-trimethylene-dipyridine (tmdp) in the absence of organic solvent and catalyst via in situ one-pot metal/ligand oxidative-dehydrogenation reactions. Large crystals have been obtained and readily separated from reaction products without the need for purification. Their structures were characterized: TPB and TPCH represent two dissimilar oxidized forms of tmdp dimers; TPCH was less oxidized but accompanied with partial hydrolysis with molecular formula further confirmed by FAB-MASS analysis. They exhibit distinct photoluminescence (PL) with quantum efficiency measured up to 42%. TPB-2 and TPB-3 are two polymorphic dihydrates, stimuli-responsive toward photoluminescence color changes; both can transform to TPB-1 upon gentle heating. Importantly, the three TPB-n crystals establish the first tetrapyridyl-type ligands adapted by metal phosphates to create a cationic luminescent framework, NTHU-12. This study serves as an inspiring route beyond conventional C–C bond formation reactions and has generated four tmdp dimers in isolation. The facile syntheses have resulted in ample production of a rare type of tetrapyridyl ligands, leading to the discovery of the first positively charged hybrid topology in nanoporous solids. The features of the four luminescent tmdp dimers and NTHU-12 embodied in synthesis, structure, and optical property are reported.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja302009h