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Pierre D. Harvey
DCpartement de chimie, UniversitC de Sherbrooke, Sherbrooke, Quebec J1K 2R1, Canada
Received June 23, 1994@
The nature of the lowest energy singlet excited state of the dIo-dlo C U ~ ( C ~ H ~ N N N C complex
~ H ~ ) ~has been
described theoretically by extended Huckel molecular orbital (EHMO) calculations and experimentally by U V -
visible, emission, and polarized emission spectroscopy. The complex is found to be fluorescent at 77 K (ZF=
2.23 k 0.03 ns, (PF= (2.7 f 0.3) x where no emission attributable to phosphorescence has been observed.
This is the first example reported in the dIo-dIo dimer family. According to the EHMO model, the lowest
w
u
L
CI:
0.974
0.730
II
0.243
0.000
200 300 400 500 600 700 800
WRVELENCTH
Figure 1. UV-visible spectra of Cuz(C&"NC6H5)2 in 2-MeTHF at 298 K (-) and at 77 K e**).The 77 K spectrum has not been corrected
for glass contraction.
-
(440 nm, E 5000 M-' cm-I; 540 nm, E 780 M-' cm-I), -
shoulders are also observed on the low-energy side of this band
-
soluble), indicating that the fluorescence must arise from a n
-
n* transition and unambiguously rules out the possible
(N=N) n n* assignment. The polarization ratios of the Cuz I
fluorescence spectrum have been measured in order to address Figure 4. EHMO energy levels for the frontier orbitals in the CUZ(C&-
the possibility of different excited states that would be respon- NNNC&):! complex. The LUMO and HOMO are MO's 74 and 75,
sible for the absorption and emission, respectively, (nn* vs respectively.
nn*),and to detect the presence of different Franck-Condon
active modes with different symmetries (if any), particularly axis is followed by emission along the same axis. N = 0.5
when the absorptivities are low in the 500 nm absorption range. indicates that single-axis absorption is followed by emission
The polarization ratio, N , is given by (ZBB/ZBE)V(ZE&B)H, where along a perpendicular axis. In practice, the theoretical values
(ZBBIZBE)~is the ratio of the intensities of vertically to horizon- were never obtained due in part to the natural depolarization of
tally polarized emission when excited with vertically polarized the glass. The experiment shows an average value of 2.8 all
light and (ZEE/ZEB)H is the ratio of the intensities of II- and along the fluorescence spectrum when the excitation is at 500
I-polarized emission with horizontally polarized excitation. N nm (Figure 3) and all along the excitation spectrum between
is then related to the relative orientation of the transition 450 and 550 nm (at Aemi = 600 nm), clearly indicating that the
moments in absorption and emission. The theoretical value of
N = 3 indicates that absorption polarized on a single molecular
emission (600 nm) is polarized parallely to the absorption (500
nm). The 500 nm absorption band is assigned to a n n*
transition. The constant N value (along the spectrum) indicates
-
(20) (a) Examules of fluorescent inorganics exist and include uomhvrin
I I , that the symmetry of the Franck-Condon active modes is the
compounds20band some iridium &mplexes.20b (b) See, for example:
Sessler, J. L.; Johnson, M. R.; Lin, T.-Y.; Creager, S. E. J. Am. Chem. same all along the progression. The graph of N vs A shows
SOC. 1988, 110, 3659. (c) Balch, A. L.; Nagle, J. K.;Oram, D. E.; some fluctuation (Le. noise) that is associated with the smaller
Reedy, P. E. J. Am. Chem. SOC. 1988, 110, 454. emission quantum yield (QF = 0.0027). The 400 nm excitation
(a) See for instance the data reported for the pt~(PoP)4~- complex, experiment was not attempted since the correspondence between
for which both emissions arising from the singlet and triplet states
are observed ( t = ~ 8 ps; kF = 2 x lo7 s-I): Stiegman, A. R.; Rice, absorption and excitation is not adequate in this region; the N
S. F.; Gray H. B.; Miskowski, V. M. Inorg. Chem. 1987, 26, 1112. values would be physically meaningless.
(b) Turro, N. J. Modem Molecular Photochemistry; Benjamin/ 3. EHMO Analysis. Two closely related compounds
Cummings: Menlo Park, CA, 1978. (c) The theoretical fluorescence
rate constant, k ~ ( I l ,can be roughly estimated using the oscillator ( M Z ( C ~ H ~ N C H N C ~ were
H ~ ) Zrecently
) investigated by SCF-
strength concept:2'bf = 4.3 x 109S E dD; k#) = 3 x 10-9D~2J~ dD. Xu-SW theoretical calculations.6 The two major differences
To estimate [ E dD, the triangle method is used where E = 780 M-I with this work are that (1) the previous calculations did not
cm-I, and the width at half maximum is 4870 cm-I extracted from
the excitation spectrum. Using DO = 20 000 cm-I, k#) = 4.6 x lo6
s-'. This crude comparison is not perfect, but the data are in the
right order of magnitude.
take into account the presence of the phenyl groups and (2) the
N3 groups exhibit free lone pairs potentially giving rise to n
n* transitions close in energy to the lowest energy absorption.
-
(a) Hubig, S. M.; Drouin, M.; Michel, A.; Harvey, P. D. Inorg. Chem. A MO diagram is generated using the EHMO model (and the
1992, 31, 5375. (b) Harvey, P. D.; Gray, H. B. Polyhedron 1990, 9,
1949. (c) Harvey, P. D.; Adar, F.; Gray, H. B. J. Am. Chem. SOC. structural data for C U ~ ( C ~ H ~ " N C ~ H ~ ) point
DZh Z;
1989, I l l , 1312. Figure 4). The LUMO (MO 74; b2") is essentially the same as
2022 Inorganic Chemistry, Vol. 34, No. 8, 1995 Harvey
x
LUMO
K-
Figure 5. MO pictures for the LUMO (74) and LUMO + 1 (73).
M0=75 ( 5au 1 E = - 1 1 , 9 1 4
X X
Lz HOMO Lz
Figure 6. MO pictures for the HOMO (75) and HOMO - 1 (76)
NO577 ( 5 b 3 ~ 3E = - 1 2 . 0 5 4
I 90
IJ-
v(cm-')
Figure 7. MO picture for MO 77 (Le. the 5b3, MO). Figure 8. Top: FT-IR spectrum of solid CUZ(C&"NC~H~)Z in the
400-1740 cm-I range (resolution 4 cm-I; 200 scans). Bottom: FT-
for M = Cu (38%) and are reasonably comparable for M = Ag Raman spectrum of solid Cu~(C.&NNNC~H5)2at 298 K. Experimental
(1 1%). The metal angular contribution is in all cases (this work conditions: resolution, 4 cm-I; number of scans, 1500; laser excitation,
and previous work6) the same (100% dq). This difference 1064 nm; laser power at the sample, 51 mW (defocused); baseline-
corrected spectrum. Proposed assignments: 1621, 1590, and 1495
cannot be easily explained and appears to be related to the
cm-I, v(CC); 1368 cm-' and a shoulder at 1340 cm-I, v(NN) (ag +
methods employed for the computations. Below the HOMO
lie two MO's (MO's 76 and 77) at O.lleV (-850 cm-') and
b3,); 1178 cm-I, v(NC) or v(CC); 516 and 413 cm-', v(CuN) (a, +
b3&. The region above 1740 cm-I was not investigated and exhibited
0.15 eV (-1210 cm-I), respectively. The former is almost only the C-H stretching bands.
exclusively composed of N px atomic orbitals (78%) which are
essentially the N lone pairs (Figure 6). Some Cu px atomic
contributions (12%) are also noted, and these promote bonding
-
the N3 centers. Therefore the n n* nature of the transition
is mixed with a minor contribution of metal-to-ligand charge
- -
interactions between the metal and the ligand. The symmetry
of this orbital is b3,,, and the lowest energy n n* transition
transfer (MLCT). Such a conclusion is supported by the larger
-
red shift of the I,, (of emission) with the medium polarity,
and cannot be easily addressed experimentally. These can be (23) There is significant overlap between the different and closely located
inverted but are of very little consequence for this work. absorption bands (Figure 1). The excitation spectra do not display
such behavior where the lowest energy band is reasonably isolated.
-
4. Franck-Condon Analysis. The lowest energy electronic
transition (au bZu) exhibits a migration of some electronic
density from both the phenyl groups and the copper metals to
The comparison between a calculated and an observed spectrum is
more appropriate in this case.
(24) Huang, K.; Rhys, A. Proc. R . SOC.London 1958, A204, 406.
2024 Inorganic Chemistry, Vol. 34, No. 8, 1995 Harvey
Chart 2
/N\N
i t
T T
N
\N/N
12 14 16 1.8 20
Wavenumber [cm-'1 xlO"
"apparent 0-0". If the true 0-0 band could have been resolved,
its intensity would not have been great. This observation
explains why no clear change in polarization ratios is observed
upon going from 550 to 600 nm. The closest peaks observed
in the IR spectra are 1368 and 480 cm-I and compare reasonably
well with the calculations. The excited state distortions (AQ)
are ~alculated'~.*~ and are 0.050 and 0.067 8, for the two modes,
respectively. These values compare favorably with the data
reported for the Ru(bp~)3~+ cation (bpy = bipyridine) for which