Direct observation of the luminescence from the (3)deltadelta excited state of Re(2)Cl(2)(p-OCH(3)form)(4).
There are only a few reports on the measurement of the energy of the low-lying (3)deltadelta state of quadruply bonded bimetallic complexes, and the direct observation of the (1)deltadelta excited electronic state was only recently reported. In the quadruply bonded bimetallic complexes reported to date, luminescence arises from their (1)deltadelta excited state, and the (3)deltadelta state is nonemissive. Here we report the luminescence of Re(2)Cl(2)(p-OCH(3)form)(4) [p-OCH(3)form = (p-CH(3)OC(6)H(4))NCHN(p-CH(3)OC(6)H(4))(-)] observed upon 400-460 nm excitation with maxima at 820 nm (CH(2)Cl(2), tau = 1.4 micros) and 825 nm (CH(3)CN, tau = 1.3 micros) at 298 K. From the large Stokes shift, the vibronic progression at 77 K, the quenching by O(2), the long lifetime, and the calculated energy of the (3)deltadelta state, the luminescence of Re(2)Cl(2)(p-OCH(3)form)(4) and the corresponding transient absorption signal are assigned as arising from the (3)deltadelta ((3)A(2u)) excited state of the complex.
Bradley
Patricia M
PM
Department of Chemistry, The Ohio State University, Columbus, Ohio 43210, USA.
Smith
Laura T
LT
Eglin
Judith L
JL
Turro
Claudia
C
D049449:Luminescence; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D012211:Rhenium / Q000737:chemistry*; D013053:Spectrophotometry / Q000379:methods; D013696:Temperature; D013816:Thermodynamics
D009942:Organometallic Compounds; D012211:Rhenium