Photophysics and Photochemistry of Copper(I) Phosphine and Collidine Complexes: An Experimental/Theoretical Investigation Page: 75
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Table 2.13 Wavelength values of temperature dependant luminescent emission spectra
of [Cu(Coll)3]PF6 powder sample in Figure 2.25 and lifetime data.
Temperature Excitation Emission Stokes Shift FWHM Lifetime ( s)
(K) Wavelength Wavelength (cm-) (cm-)
(nm) (nm)
77 319 454 9421 3713 46.9 + 0.6
90 318 453 9371 3753 47.3 + 0.5
120 318 453 9371 3753 44.3 + 0.6
180 326 450 8453 3941 40.8 + 0.5
210 327 448 8260 4034 36.5 + 0.6
250 340 444 6889 4327 31.5 + 0.6
298 345 437 6102 4508 20.2 + 0.5
The [Cu(Coll)3]PF6 powder is shown to have blue emission from 77 K to 298 K
temperatures to the naked eye. As the complex is warmed from 77K to 298 K the
intensity of the emission is seen to slightly diminish, as warming the complex will cause
more nonradiative emissions (such as geometric distortions and vibrations) to increase,
thus less radiative emission are observed. The emission appears to blue shift (17 nm)
as the complex is warmed. As was previously mentioned in above sections, as the
complex warms, thermal broadening occurs (FWHM 77K=3713 cm- versus 298K=4508
cm-) causing the emission energy to be slightly blue shifted compared to emissions
seen at 77K.75
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Determan, John J. Photophysics and Photochemistry of Copper(I) Phosphine and Collidine Complexes: An Experimental/Theoretical Investigation, dissertation, August 2011; Denton, Texas. (https://digital.library.unt.edu/ark:/67531/metadc84199/m1/96/: accessed April 28, 2024), University of North Texas Libraries, UNT Digital Library, https://digital.library.unt.edu; .