Solid state emission spectra

Figure 5.15 Room-temperature solid-state emission spectra of [Au2(dcpm)2]X2 (X = CF3S03, Au(CN)2, CI , and T) with excitation at X = 280nm. I = intensity Reproduced with permission from [6b]. Copyright (2001) Wiley-VCH.

The first copper(I) complex of tris(hydroxymethyl)phosphine ((760) tetrahedral) has been reported by Samuelson and co-workers. This group addressed the question of anion-controlled nuclearity and metal-metal distances in copper(I)-bis(diphenylphosphino)methane complexes, and in this endeavor they reported the structures of complexes (761) (Cu-Cu separation 3.005-3.128 A), (762) (Cu-Cu separation 3.165 A) and (763) (tetrahedral Cu-Cu 3.293 A). 6 They synthesized and provided structural evidence of oxy anion- encapsulated copper(I) complexes of this ligand. The complexes (764) (distorted tetrahedral Cu-Cu 3.143 A), (765) (distorted tetrahedral Cu-Cu 3.424A), (766) (distorted trigonal Cu-Cu 3.170A), and (767) (Cu-Cu 3.032-3.077A) were reported. They studied solid-state emission spectra of these complexes.567 During this pursuit they... 

The electronic spectra for the new mixed-ligand ID polymers exhibit an absorption band at 272 nm, assigned to a MLCT (rather than ira arising from the phenyl group). Solid-state emission spectra were recorded for both the model compounds and the polymers. The luminescence appears as broad bands located between 480 and 550 nm. Large Stokes shifts were observed, and the corresponding emission lifetimes (t6) ranged between 18 and 48 i,s (Table 4). These experimental data indicate that these emissions are in fact phosphorescence. 

FIGURE 11. Solid-state emission spectra of supramolecular isomers 7a,b recorded at ambient temperature with maxima at — 538 and 636 nm after excitation at 260 nm, respectively. (Modified from Ref. 127.)... 

As expected, both materials 9 and 10 exhibit interesting luminescence properties. The superposed solid-state emission spectra of 9 and 10 are depicted... 

FIGURE 16. Normalized superimposed solid-state emission spectra recorded at room temperature for isostructural compounds 9 (solid line) and 10 (dotted line) after excitation at 360 nm. 

FIGURE 23. Normalized solid-state emission spectra of 14 (a) and 15 (b) recorded at ambient temperature, featuring maxima at 414, 435, and 550 nm, respectively ( excit = 360 nm). X denotes an emission at 414 nm due to some traces of compound 14 as impurity in the sample of 15. 

FIGURE 53. Solid-state emission spectra of ID polymer [Cu4I4(L47)2(MeCN) (C6H14)] 47, recorded at 298 K and 77 K after excitation at 286 nm. (Modified from Ref. 166.)... 

Fig. 7 Solid-state emission spectra of 22(C104) at 298 and 77 K (lex 350 nm, normalized intensities) (Reproduced with permission from [20]. Copyright 2002 American Chemical Society)...

Fig. 8 Normalized solid-state emission spectra of (dotted line) orange 16(BF4)3, (dashed line) red, and (continuous line) brown-red forms of 16(C104)3 at 298 K...

The 77 K emission of [M2(C ANAN)2(/U-dppm)]2+ in frozen CH3CN occurs at /Lmax 598 and 638 nm for M=Pd 20 and Pt 7b respectively (Fig. 15). Since a n-n excimeric 3IL excited state is invoked for the Pd2 species, the red shift for the Pt2 analogue is indicative of an excited state arising from n-n (excimeric 3IL) and metal-metal (previously assigned as da —>7r ) interactions. The 77 K solid-state emission spectra for [M2(ClANAN)2(/t-dppm)](C104)2... 

Figure 4.25 Solid-state emission spectra of 69 and 70 at 298 K. Modified from reference [60]...

Figure 7 Solid-state emission spectra of 41a, 41b, and 41c at 298 K. (Adapted from Ref. [69].)...

FIGURE 9. (a) View of the core unit of 2D polymer [ Cu( i-I)2Cu (dps)2] (5). (b) Solid-state emission spectrum of 5 recorded at ambient temperature. (Modified from Ref. 125.)... 

In contrast, the fluorescence of PTPAF lb closely resembles its solution spectrum, with maxima at 428 run (2.90 eV) and 452 nm (2.74 eV), and no peak in the low-energy region. The same is true for the solid state emission spectrum of PBPF (Ic), i.e., another PF polymer with bulky side groups, which shows a peak at 457 nm (2.71 eV, pure blue emission), with no emission in the low-energy region. 

Figure 4.7 UV-vis spectrum (left) in MeCN and solid state emission spectrum (right) for 42 at 298 K. (Modified from reference [45])...

Therefore, this low-energy band is assigned to a metal-centered d->p transition instead of as arising from Au---Au interactions. The solid-state luminescence spectrum (Fig. 25) exhibits a phosphorescence emission band centered at 417 nm. This value compares favorably with those reported for solids K[Au(CN)2]58 and Au2(dmb)(CN)2.63... 

In line with the variation of the Cu Cu interaction in function of the temperature, the emission maximum in the solid-state luminescence spectrum (Nxcit = 350 nm) of 47 appears considerably red shifted when the temperature is decreased from 298 K (538 nm) to 77 K (599 nm). The red shift is less pronounced in the case of compound 47" Figure 53 reveals that the low-temperature spectrum is somewhat less broadened than that recorded at room temperature. 

Fig. 74 shows the IR emission spectrum of the transition of K2TaF7 from solid to molten state. 

The electroluminescence spectra of the single-layer devices are depicted in Figure 16-40. For all these OPV5s, EL spectra coincided with the solid-state photoluminescence spectra, indicating that the same excited states are involved in both PL and EL. The broad luminescence spectrum for Ooct-OPV5-CN" is attributed to excimer emission (Section 16.3.1.4). 

The reaction with PPh2CCH leads to the formation of [Au(QF5)(PPh2CCH)[ [53] whose P H NMR spectrum shows a singlet at 17.2ppm, in the H NMR spectrum the resonance of the C = CH proton is observed at 3.46 ppm. The IR spectrum shows, besides the pentafluorophenyl absorptions, a band at 3271 cm due to the V(Csch) and another absorption at 2056 cm for the asymmetric C = C stretch. The structure of this complex was studiedby X-ray diffraction, the Au(I) atom is an almost linearly coordinated and the Au—C and Au—P distances are in the range of the values found for similar complexes. The excitation and the emission data in the solid state at 77 K are 331 and 445 nm. 

Figure 2.66 The X-ray emission spectrum of copper. From A.R. West, Solid State Chemistry and its Applications, John Wiley and Sons, Chichester (1984). Reprinted by permission of John...

Figure 5.1 Resonant absorption of y-radiation by a nucleus can only take place in the solid state because of recoil effects. The excited nucleus of a free atom emits a y-photon with an energy EirER, whereas the nucleus in the ground slate of a free atom can only absorb a photon if it has an energy equal to Eo+ER. As the linewidth of nuclear transitions is extremely narrow, the emission spectrum does not overlap with the absorption spectrum. In a solid, a considerable fraction of events occurs recoil free (ER=0), and here the emission spectrum overlaps completely with the absorption spectrum (provided source and absorber have the same chemical environment).

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