Electronic spectra properties

In order to discuss electron transport properties we need to know about the electronic distribution. This means that, for the case of metals and semimetals, we must have a model for the Fermi surface and for the phonon spectrum. The electronic structure is discussed in Chap. 5. We also need to estimate or determine some characteristic lengths. 

The reduced symmetry of the chromophore, which still contains 187t-electrons and is therefore an aromatic system, influences the electronic spectrum which shows a bathochromic shift and a higher molar extinction coefficient of the long-wavelength absorption bands compared to the porphyrin, so that the photophysical properties of the chlorins resulting from this structural alteration render them naturally suitable as pigments for photosynthesis and also make them of interest in medical applications, e.g. photodynamic tumor therapy (PDT).2... 

In a solution where a nonzero volume change between the electronic isomers, HS and LS, is encountered, the position of the spin equilibrium will depend on pressure. The volume change, usually denoted here AF°, may be obtained from the study of the pressure dependence of equilibrium properties such as the magnetic susceptibility or the electronic spectrum. In favorable cases, A F° values may be derived from the amplitude of sound absorption observed in ultrasonic relaxation measurements of a spin equilibrium as will be shown in the... 

Stable Mn(HI) compounds, Mn(R2r fc)3, have been known for a long time (42, 46). The structure of Mn(Et2C tc)3 is elucidated (47). The inner geometry of the Mn(CS2)3 core does not conform to the usual D3 point symmetry of transition metal complexes of this type, but shows a strong distortion attributed to the Jahn-Teller effect. The electronic spectrum (48, 49) and the magnetic properties of this type of complexes are well studied (50). 

The broad PL emission spectra of some metal chelates match the requirements for white emission. Hamada et al. investigated a series of Zn complexes and found bis(2-(2-hydroxy-phenyl)benzothiazolate)zinc (Zb(BTZ)2, 246) is the best white emission candidate. An OLED with a structure of ITO/TPD/Zn(BTZ)2/OXD-7/Mg In showed greenish-white emission with CIE (0.246, 0.363) with a broad emission spectrum (FWHM 157 nm) consisting of two emission peaks centered at 486 and 524 nm (Figure 3.14) [277], A maximum luminance of 10,190 cd/m2 at 8 V was achieved. The electronic and molecular structure of Zn(BTZ)2 have been elucidated by Liu et al. [278]. There is evidence that the dimeric structure [Zn(BTZ)2]2 in the solid state is more stable than its monomer Zn(BTZ)2. They also found that the electron transport property of Zn(BTZ)2 is better than that of Alq3. 

The spectrum of the ester 73c is similar to that of the unsubstituted phenyl compound 73e (both not shown). It is noted that the chemical shift of the HC8 reflects the electron-withdrawing properties of the substituents. A combination of ID and 2D techniques is used to establish the assignments shown, and the chemical shift changes as compared to /J,/J-carotene are listed in Tables 22 and 23. 

N-Do/Jor Ligands. The full account of the preparation and properties of V[N(SiMc3)2]3 has been published. (Et4N)3[V(NCSe)e] has been prepared and its electronic spectrum reported in several solvents. The electronic spectra of fVL lfNCSij complexes (L = py, 3-picoline, 3,4-lutidine, or 3,5-lutidine) are consistent with tetrahedral microsymmetry about the V " atom, and the magnetic properties of V complexes with the thiosemicarbazones of salicylaldehyde and pyruvic acid have been interpreted in terms of a tetragonal environment about the metal. ... 

The emission from [Ru(bpz)3] is quenched by carboxylic acids the observed rate constants for the process can be rationalized in terms of the protonation of the non-coordinated N atoms on the bpz ligands. The effects of concentration of carboxylate ion on the absorption and emission intensity of [Ru(bpz)3] have been examined. The absorption spectrum of [Ru(bpz)(bpy)2] " shows a strong dependence on [H+] because of protonation of the free N sites the protonated species exhibits no emission. Phosphorescence is partly quenched by HsO" " even in solutions where [H+] is so low that protonation is not evidenced from the absorption spectrum. The lifetime of the excited state of the nonemissive [Ru(Hbpz)(bpy)2] " is 1.1ns, much shorter than that of [Ru(bpz)(bpy)2] (88 nm). The effects of complex formation between [Ru(bpz)(bpy)2] and Ag on electronic spectroscopic properties have also been studied. Like bpz, coordinated 2,2 -bipyrimidine and 2-(2 -pyridyl)pyrimidine also have the... 

Although the electronic spectrum of a molecule should be most directly correlated with theory, there are several other physical properties which can be related, if only qualitatively, to the bond theory of the molecule. We shall discuss some of these now. 

A polymer containing anthracene, [Ru(bpy)3]2 , and [Os(bpy)3]2+ [all covalently linked to a 1 1 copolymer of styrene and m,p-(chlorome-thyl)styrene] has been prepared, and its emission spectrum and intramolecular electron-transfer properties have been studied (569). 

The electronic and magnetic properties of vanadium tetramethoxide are consistent with a trimeric structure involving six-coordinate vanadium atoms, while the electronic spectrum of deep blue V(OBu )4 is consistent with a slightly distorted monomeric, tetrahedral structure.181... 

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