Structural, photophysical, and nonlinear absorption properties of trans-di-arylalkynyl Platinum(II) Complexes with Phenyl and Thiophenyl Groups

Optical power limiting and luminescence properties of two Pt(II) complexes with thiophenyl and phenyl groups in the ligands, trans-Pt(P(n-Bu)3)2(C[triple bond]C-Ar)2, where Ar = -C4H2S-C[triple bond]C-p-C6H4-n-C5H11 (1) and -p-C6H4-C[triple bond]C-C4H3S (2), have been investigated. The fluorescence lifetimes were found to be on the sub-nanosecond time scale, and the quantum yields were low, in accord with fast intersystem crossing from the excited singlet to triplet manifold. The phosphorescence lifetimes of 1 and 2 were shorter than that of a Pt(II) complex having two phenyl groups in the ligands. In order to elucidate the C-Pt bonding nature in the ground state, the 13C NMR chemical shift of the carbon directly bonded to Pt, the coupling constants 1JPtC, 2JPtC, and 1JPtP, and IR νC[triple bond]C wavenumbers were obtained for 1, 2, and three other trans-diarylalkynyl Pt(II) complexes. X-ray diffraction data of 1 and 2 and density functional theory calculated geometries of models of 1, 2, and trans-Pt(P(n-Bu)3)2(C[triple bond]C-p-C6H4-C[triple bond]C-C6H5)2 (3) show that 1 preferably exists in a different conformation from that of 2 and 3. The variations in photophysical, NMR, and IR data can be rationalized by differences in geometry and pi-backbonding from Pt to the alkynyl ligand.

Boström, DanUmeå universitet,Kemiska institutionen(Swepub:umu)dabo0001 (författare)
Carlsson, MarcusUmeå universitet,Energiteknik och termisk processkemi(Swepub:umu)mascan97 (författare)
Eriksson, Anders (författare)
Glimsdal, Eirik (författare)
Lindgren, Mikael (författare)
Eliasson, BertilUmeå universitet,Energiteknik och termisk processkemi(Swepub:umu)beel0001 (författare)
Umeå universitetEnergiteknik och termisk processkemi (creator_code:org_t)

Ingår i:Journal of Physical Chemistry A: American Chemical Society (ACS)111:9, s. 1598-16091089-56391520-5215

Av författaren/redakt...: Lind, Per; Boström, Dan; Carlsson, Marcus; Eriksson, Anders; Glimsdal, Eirik; Lindgren, Mikael; visa fler...; Eliasson, Bertil; visa färre...

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