Molecular luminescence

Yam VW-W, Wong KM-C (2005) Luminescent Molecular Rods - Transition-Metal Alkynyl Complexes. 257 1-32... 

As in the case of the 1,2-dioxins, the 1,2-dithiins exist in various states of saturation, oxidation, and benzoannelation (cf. Scheme 1, 17-27) and they have been studied in detail both theoretically and experimentally. Not only were the conformations of the ring and attached substituents investigated, but the valence isomerism of 1,2-dithiin by both NMR and high-level ab initio molecular orbital (MO) calculations and the dithiol/disulfide equilibrium by MP2 calculations were also examined. The latter equilibrium has been applied successfully as a luminescent molecular switch (cf. Section 8.10.2.1). Finally, as a very interesting 1,2-dithiin derivative, the synthesis, structure, and reactivity of the (-l-)-camphor-derived analog 25 and its sulfoxide 26 and sulfone 27 have been reported. Both the synthesis and the antimalarial activity of the 2,3-dioxabicyclo[3.3.1]nonane pharmacophore 28, which contains the 1,2-dioxane moiety, have been reviewed recently <2006BML2991>. 

Of note, the dithiol/disulfide equilibrium (Scheme 6) has been successfully employed as a luminescent molecular switch <2006CEJ689>. 

Gunnlaugsson, T. Donall, A. M. D. Parker, D. Luminescent molecular logic gates the two-input inhibit (INH) function. Chem. Commun. 2000, 93-94. 

Crystal-field spectroscopy of dn ions is being extended nowadays to the near-infrared region with interesting results. Vibronic structure is nowadays used to obtain information on the deformation of the excited state. Also in case of the closed-shell d° complexes the excited state appears to be strongly distorted. Among the latter class especially the linear species show efficient luminescence. Molecular-orbital calculations are in progress and will probably yield interesting results. 

Luminescent molecular signaling systems usually serve two general needs gathering information (preferably continuously) from small and fragile spaces,... 

A substantial number of interesting luminescent molecular systems contain cy-clophane receptor units [110] and involve PET-type processes, particularly as a result of the collaboration between the teams of Stoddart (now at the University of California at Los Angeles) and Balzani (University of Bologna, Italy) [111]. 

Rogers CW, Wolf MO. Luminescent molecular sensors based on analyte coordination to transition-metal complexes. Coord Chem Rev 2002 233-234 341-50. 

Figure 16.4 Principle of the PCT (photoinduced charge transfer), chemically driven, luminescent molecular sensor based on the donor-spacer-acceptor architecture, (a) Binding of analyte trigger to the donor (green) moiety results in hypsochromic shift of absorption (emission) band (b) binding of the same analyte to the acceptor moiety (red) results in bathochro-mic shift of corresponding transition...

Gunnlaugsson, T., Donaill, D.A.M., and Parker, D. (2001) Lanthanide macrocyclic quinolyl conjugates as luminescent molecular-level devices. Journal of the American Chemical Society, 123, 12866-12876. 

T. Gunnlaugsson, D. A. M. DonaiU, D. Parker, Lanthanide Macrocyclic Quinolyl Conjugates as Luminescent Molecular-Level Devices , J. Am. Chem. Soc., 123, 12866 (2001)... 

Luminescence molecular detectors have also been used for on-line monitoring of dissolution tests and the characterization of toxic residues using bioluminescence assays [28]. 

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