Re(I) Complexes of Substituted dppz: A Computational and Spectroscopic Study
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https://figshare.com/articles/dataset/Re_I_Complexes_of_Substituted_dppz_A_Computational_and_Spectroscopic_Study/2314531
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资源简介：
A series of dipyrido[3,2-a:2′,3′-c]phenazine (dppz)-based
ligands with electron-withdrawing
substituents and their [Re(CO)3(L)Cl] and [Re(CO)3(L)(py)]PF6 complexes have been studied using Raman, resonance
Raman, and transient resonance Raman (TR2) and time-resolved
infrared (TRIR) spectroscopic techinques in conjunction with computational
chemistry as well as electrochemical studies, emission, and absorption
of ground and excited states. DFT (B3LYP) frequency calculations show
good agreement with nonresonant Raman spectra, which allowed these
to be used to identify phenanthroline, phenazine, and delocalized
modes. These band assignments were used to establish the nature of
chromophores active in resonance Raman spectra, probed with wavelengths
between 350.7 and 457.9 nm. X-ray crystallography of [Re(CO)3(dppzBr2)Cl] and [Re(CO)3(dppzBr)(py)]PF6 showed these crystallize in space groups triclinic P1 and monoclinic P21/n, respectively. Electrochemical studies showed that substituents
have a strong effect on the phenazine MO, changing the reduction potential
by 200 mV. Transient absorption studies showed that generally the
[Re(CO)3(L)(py)]PF6 complexes had longer lifetimes
than the corresponding [Re(CO)3(L)Cl] complexes; the probed
state is likely to be 3π → π* (phz)
in nature. TR2 spectra of the ligands provided a marker
for the triplet π → π* state, and the TR2 spectra of the complexes suggest an intraligand (IL) π,π*
state for [Re(CO)3(L)(py)]+ complexes, and a
potentially mixed IL/MLCT state for [Re(CO)3(L)Cl] complexes.
TRIR spectroscopy is more definitive with THEXI state assignments,
and analysis of the metal–carbonyl region (1800–2100
cm–1) on the picosecond and nanosecond time scales
indicates the formation of MLCT(phen/phz) states for all [Re(CO)3(L)Cl] complexes, and IL π → π* (phen)
states for all [Re(CO)3(L)(py)]+ complexes,
with all but [Re(CO)3(dppzBr(CF3))(py)]+ showing some contribution from an MLCT(phen) state also.
创建时间：
2016-02-18
