NDLI: Design and synthesis of luminescence chemosensors based on alkynyl phosphine gold( I)

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	He, Xiaoming Yam, Vivian Wing-wah Zhu, Nianyong
Description	Author Affiliation: He X ( Institute of Molecular Functional Materials, Areas of Excellence Scheme, University Grants Committee, Hong Kong, PR China.)
Abstract	Receptor -containing polynuclear mixed-metal complexes of gold( I) – copper( I) 1–3 based on a $[\{Au_{3}Cu_{2}(C\&\#8801;CPh)_{6}\}Au_{3}\{PPh_{2}–C_{6}H_{4}–PPh_{2}\}_{3}]^{2+}$ ( Au $_{6}Cu$ $_{2}$ ) core with benzo-15-crown-5 , oligoether and urea binding sites were designed and synthesized, respectively. These complexes exhibited remarkably strong red emission at ca. 619–630 nm in dichloromethane solution at room temperature upon photoexcitation at λ > 400 nm, with the emission quantum yield in the range 0.59–0.85. The cation-binding properties of 1 and 2 and the anion-binding properties of 3 were studied using UV-vis , emission and $^{1}H$ NMR techniques. Complex 1, with six benzo-15-crown-5 pendants, was found to show a higher binding preference for K $^{+}$ , with a selectivity trend of K $^{+}$ ≫ Cs $^{+}$ > Na $^{+}$ > Li $^{+}$ . The addition of metal ions ( Li $^{+}$ , Na $^{+}$ , K $^{+}$ and Cs $^{+}$ ) to complex 1 led to a modest emission enhancement with a concomitant slight blue shift in energy and well-defined isoemissive points, which is attributed to the rigidity of the structure and the inhibited PET (photo-induced electron transfer ) process from the oxygen to the aggregate as a result of the binding of the metal ion. The six urea receptor groups on complex 3 were found to form multiple hydrogen bonding interactions with anions, with the positive charge providing additional electrostatic interaction for anion-binding. The anion selectivity of 3 follows the trend $F^{−}$ > Cl $^{−}$ ≈ H $_{2}PO$ $_{4}$ $^{−}$ > Br $^{−}$ and the highest affinity towards $F^{−}$ is attributed to the stronger basicity of $F^{−},$ as well as its good size match with the cavity of the urea pocket.
ISSN	14779226
Issue Number	38
Volume Number	40
e-ISSN	13645447
Journal	Dalton Trans.
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2011-10-14
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Alkynes Chemistry Copper Fluorescent Dyes Gold Organometallic Compounds Phosphines Crystallization Crystallography, X-Ray Chemical Synthesis Models, Molecular Molecular Structure Stereoisomerism Journal Article Research Support, Non-U.S. Gov't
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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