Korovin Y. Complex compounds of lanthanides with macro-cyclic ligands. Luminescent properties in infra-red region

Object of investigation: complex compounds of lanthanides with polydentate macrocyclic ligands. Aim of investigation: determination of the factors influencing on the IR-luminescence of lanthanide ions at their complexation with macrocyclic ligands. Methods of investigation: elemental analysis (analyser CHN-3), thermogravimetric analysis (derivatograph Q-1500 D), IR spectroscopy (spectrophotometer Specord IR-75) UV spectroscopy (spectrophotometer Perkin-Elmer Lambda 9), NMR spectroscopy (spectrometer Brucker AM-400), mass-spectrometry (spectrometer Varian MAT CH-112), luminescence spectroscopy (spectrometers SDL-1, Perkin-Elmer LS-50B). Theoretical and practical results, novelty: more than 200 new complex compounds of lanthanides with polydentate macrocyclic ligands of different classes (crown-ethers, cryptands, Schiff bases, calix[n]arenes, porphyrins, 1,4,7,10-tetraazacyclododeca-ne derivatives) have been received. By example of ytterbium cryptates and neadymium complexes with hexa- and octadentate macrocyclic Schiff bases it has been established the relation between 4f-luminescence intensity and quantity of heteroaromatic fragments (which coordinate with Ln3+ ions by means of donor atoms). For solutions of complex compounds of lanthanides it has been discovered the sensibilization of IR-luminescence of Nd3+ ions in presence of Sm3+, Eu3+, Tb3+ ions, and Yb3+ in presence Sm3+ and Nd3+ in heterometallic binuclear complexes with para-tert-butylcalix[8]arene). The relation between values of quantum yield of 4f-luminescence and parameters featuring the nature of meso-substituents in porphyrins has been established with the use of QSPR-EMMA and DRAGON methods. It has been shown that IR-luminescence of ytterbium ions into heterometallic Na(K, Cs)-Yb complexes with meso-tetrasubstituted crown-porphyrins has high values of quantum yield. It has been obtained the new type of d-f-heterometallic porphyrin complexes. It has been established that ytterbium complexes with porphyrins, containing N-heteroaromatic substituents in meso-positions, are the most promising as IR-luminescent markers from the viewpoint of diagnostic application at malignant tumours. Degree of application: pre-clinical investigations in Institute of neurosurgery of AMS of Ukraine (Kiev). Field of application: inorganic chemistry, diagnostic medical preparation