Terbium properties

Although rare-earth ions are mosdy trivalent, lanthanides can exist in the divalent or tetravalent state when the electronic configuration is close to the stable empty, half-fUed, or completely fiUed sheUs. Thus samarium, europium, thuUum, and ytterbium can exist as divalent cations in certain environments. On the other hand, tetravalent cerium, praseodymium, and terbium are found, even as oxides where trivalent and tetravalent states often coexist. The stabili2ation of the different valence states for particular rare earths is sometimes used for separation from the other trivalent lanthanides. The chemicals properties of the di- and tetravalent ions are significantly different. 

Lanthanum and samarium show virtually no NO dissociation activity even in the presence of Pt. These supports are not reducible and have no OSC property. The intrinsic NO dissociation activity of platinum is very weak, probably in reason of the low metal dispersion. The behavior of terbium oxide is more surprising. Although it is reducible in H2, it is unable to dissociate NO except in the presence of Pt. 

Until very recently, studies of the use of luminescent lanthanide complexes as biological probes concentrated on the use of terbium and europium complexes. These have emission lines in the visible region of the spectrum, and have long-lived (millisecond timescale) metal-centered emission. The first examples to be studied in detail were complexes of the Lehn cryptand (complexes (20) and (26) in Figure 7),48,50,88 whose luminescence properties have also been applied to bioassay (vide infra). In this case, the europium and terbium ions both have two water molecules... 

Organic fluorescent dyes with the appropriate spectral properties also can be paired with lanthanide chelates in FRET systems. For instance, many rhodamine dyes and the cyanine dye Cy5 have ideal excitation wavelengths for receiving energy from a nearby europium chelate. The LeadSeeker assay system from GE Healthcare incorporates various Cy5-labeled antibodies for developing specific analyte assays. In addition, if using a terbium chelate as the donor, then a Cy3 fluorescent dye can be used in assays as the acceptor. 

The halogens (group VIIA) of terbium are strong irritants. Most of the compounds are toxic and some are explosive. A vacuum or inert atmosphere must be maintained when working with the metal because of its strong oxidation properties. 

Carl Gustaf Mosander, a Swedish chemist, successfully separated two rare-earths from a sample of lanthanum found in the mineral gadolinite. He then tried the same procedure with the rare-earth yttria. He was successful in separating this rare-earth into three separate rare-earths with similar names yttia, erbia, and terbia. For the next 50 years scientists confused these three elements because of their similar names and very similar chemical and physical properties. Erbia and terbia were switched around, and for some time the two rare-earths were mixed up. The confusion was settled ostensibly in 1877 when the chemistry profession had the final say in the matter. However, they also got it wrong. What we know today as erbium was originally terbium, and terbium was erbium. 

Berkelium is a metallic element located in group 11 (IB) of the transuranic subseries of the actinide series. Berkelium is located just below the rare-earth metal terbium in the lanthanide series of the periodic table. Therefore, it has many chemical and physical properties similar to terbium ( Tb). Its isotopes are very reactive and are not found in nature. Only small amounts have been artificially produced in particle accelerators and by alpha and beta decay. 

The rare earth oxides have a number of distinguishing properties important in catalytic applications. The oxides are basic O) compared to alumina, lanthanum oxide (La203) being the most basic. The oxides also have good thermal stability, a valuable characteristic in most industrial applications. Some rare earths including cerium, praseodymium, and terbium form non-stoichiomet-ric oxides ( ), an important property shared by many good oxidation catalysts. These mixed valence state compounds are typically polymorphic. 

The unsymmetrical derivative, L2, in which one benzimidazole group is replaced by a 2-pyridyl moiety, and its complexes with europium and terbium have been further studied for their photophysical properties (37). The coordinated nitrate anions in the [ ( 2)( ) ]... 

Photophysical studies have been conducted on a number of lanthanide complexes of calix[n]arenes, and a significant number of these are discussed in a recent review (79). The first europium and terbium calixarene complexes showed promising photophysical properties, with terbium luminescence lifetime of 1.5 ms and quantum yield of 0.20 in aqueous solution (80). 

Mono- and bimetallic lanthanide complexes of the tren-based macrobicyclic Schiff base ligand [L58]3- have been synthesized and structurally characterized (Fig. 15), and their photophysical properties studied (90,91). The bimetallic cryptates only form with the lanthanides from gadolinium to lutetium due to the lanthanide contraction. The triplet energy of the ligand (ca. 16,500 cm-1) is too low to populate the terbium excited state. The aqueous lifetime of the emission from the europium complex is less than 0.5 ms, due in part to the coordination of a solvent molecule in solution. A recent development is the study of d-f heterobimetallic complexes of this ligand (92) the Zn-Ln complexes show improved photophysical properties over the homobinuclear and mononuclear complexes, although only data in acetonitrile have been reported to date. 

Glasses. Pearson and Peterson 98) studied extensively the fluorescent decay properties of terbium in Calibo base glass which has the composition CaO, 20 Li20, 10 B203, 70 mole per cent. All their data was taken using a stroboscopic method. 

Ionic radius TbJ+ 0,93 A, Tb4+ 0.76 A. Metallic radius 1.783 A. First ionization potential 5.84 eV second 11.52 eV, Other physical properties of terbium are given under Rare-Earth Elements and Metals. See also Chemical Elements. 

Fluorescent probes in reversed micellar aggregates proved, moreover, appropriate to study dynamic properties of micelles in nonpolar solvents42,44 The particularly suitable fluorescent label was the highly water sensitive terbium ion (Tb3+) (Fig. 26). 

Parker and Williams recently reported NAND logic action in the terbium complex 16.[S8] The delayed emission of the lanthanide ion is switched off when H+ and 02 are present simultaneously. Protonation of the phenanthridine side chain causes its triplet excited state to approach theTb(m) 5D4 excited state energetically. This leads to equilibration of these two excited states and sharing of their properties. Thus, the metal-centered state displays the 02 sensitivity usually only found in organic triplets. 

Several review articles and books on the lanthanide higher oxides, which include thermodynamic properties, have been published (Eyring, 1979 Haire and Eyring, 1994 Trovarelli, 2002 Adachi and Imanaka, 1998 Adachi et al., 2005). The systematic thermodynamic data of the cerium, praseodymium, and terbium oxides can be found in Bevan s and Eyring s papers (Hyde et al., 1966 Hyde and Eyring, 1965 Bevan and Kordis, 1964). 

Another example of a different type of correlation of structural to photophysical properties is shown in a study of a unique terbium compound [63]. This compound will be briefly discussed and is depicted in Figure 7.9 with its nonlinear emission properties with excitation at 800 nm. The photophysical properties are atypical and rather extraordinary due to the unusual molecular structure of the co-crystallization compound (4) of the organic chromophore and the terbium salt This compound shows both multiphoton absorption induced green f-f emission from the terbium ion as well as second-harmonic generation. However, unlike previously... 

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