Exploiting lanthanide luminescence in supramolecular assemblies

Abstract

Lanthanide ions, due to their unique photo-physical characteristics, have attracted considerable attention in recent years. Their long lifetimes, sharp, well-defined emission bands, and designable environmental sensitivity make them ideal for integration into switchable supramolecular assemblies where emission can report on local conformation and/or coupled energy levels (redox state). The immobilisation of lanthanide containing constructs on interfaces facilitates device integration, the fabrication of advanced sensory and molecular electronic platforms and presents a means by which conformational dynamics within molecular assemblies can be analysed. In this feature article we discuss the current and potential applications for lanthanide luminescence in supramolecular, switchable and surface bound architectures.

Lanthanoid/Alkali Metal β‐Triketonate Assemblies: A Robust Platform for Efficient NIR Emitters

“…The luminescentp roperties of the lanthanoid trivalent cations are useful in aw ide range of applications. [1][2][3][4][5][6][7] In particular, complexes of these elements that exhibit emission in the nearinfrared (NIR) region have been highly soughtafter in biomedical areas [2,[8][9][10] because NIR photons offer deeper tissue penetrationa nd are less affected by scattering. [11] NIR emission is also used in opticald evices,s uch as night-vision technology, and in telecommunications.…”

New Fluorenocrownophanes with Naphthalene Fragments: Synthesis, Structure, Properties and Interaction with Paraquat

“…Fluorenonocrownophanes 1a-c,e-g, [17][18][19] and paraquat bis(hexafluorophosphate) 6·2PF 6 [20] were obtained by previously described procedures. 8,11,14,17,20,23,35,38,41,44,47,7 .1 24,28 .1 30,34 .0 4,54 .0 27,31 ]octapentaconta-1(55), 3(58), 4,6, 24(57), 25,27,30(56), 31,33,51,53-dodecaen-2,29-dione (1d). To a suspension of 5.52 g (0.04 mol) of anhydrous potassium carbonate in 600 mL of dry DMF was added with stirring a solution of 0.01 mol of 2,7-dihydroxyfluorenone and 0.01 mol of the corresponding bistosylate [17] in 400 mL of dry DMF.…”

“…[1][2][3] The practical goal of these studies was to create novel compounds that are able to form strong complexes with electron-deficient substrates which can then be used to construct supramolecular and sensor systems. [4][5][6][7] The fluorene moiety, as well as its derivative fluorenone, has a large π-electron system and the removal of the carbonyl group results in increased electron density and the uniformity of its distribution. The methylene protons in position 9 can act as a "probe" as they are situated out of the plane of the aromatic rings and should be most sensitive to the spatial environment changes of the molecule, which can be used for study of complexation properties by NMR.…”

Surface-based molecular self-assembly: Langmuir-Blodgett films of amphiphilic Ln(III) complexes

“…Trivalent lanthanide ions have readily manipulated coordination environments and interesting photophysical properties (e.g. sharp, long-lived emission at long wavelengths) making them particularly useful in molecular recognition and sensing [1–5]. The majority of studies have been carried out in solution, however to progress towards practical, robust and commercialised sensing applications (e.g.…”