Syntheses, Characterization, and Photophysical Properties of Conjugated Organometallic Pt-Acetylide/Zn(II) Porphyrin-Containing Oligomers

摘要: Two conjugated organometallic oligomers of the type (-C[triple bond]CPt(L)(2)C[triple bond]C(ZnP)-)(n) and model compounds [PhC[triple bond]C(ZnP)C[triple bond]CPh] with L = tri(n-butyl)-phosphine ZnP zinc(II)(10,20-bis(Ar)porphyrine) (Ar mesityl (Mes; P1 M1) or 3,4,5-trihexadecyloxyphenyl (P2 M2)) were synthesized characterized ((1)H (31)P NMR, HRMS, elemental analysis, IR, GPC, TGA). GPC indicates that P2 exhibit respectively approximately 6 3 units a polydispersity 1.4. M1 was also by X-ray crystallography. The Pt...Pt separation in is 1.61 nm, which makes 9.6 nm long. spectral measurements show absorption photoluminescence spectra M1, M2, P1, are remarkably red-shifted. For example, low energy Q-band observed at 677 +/- 1 comparison their precursors HC[triple bond]CH, L1 L2 L1) (L2)), both 298 77 K, for 622 nm. photophysical parameters, fluorescence lifetimes (tau(F)), quantum yields (Phi(F)) slight decrease factor 2 (at most 3) following trend > M2 P2, explained combination heavy atom effect an increase internal conversion rate due to oligomer dimension. This small variation data materials few dimension contrasts larger change tau(P), phosphorescence Pt-containing unit (-C(6)H(4)C[triple bond]C-CC(6)H(4)(ZnP)-)(n) n 3, 6, 9 reported earlier (Liu, L.; Fortin, D.; Harvey, P. D. Inorg. Chem. 2009, 48, 5891-5900). In this later case, tau(P) decreased steps order magnitude as increased from 9. T(1) transfer Pt (donor) MP (acceptor) excitonic process (energy delocalization). Because full conjugation these behave distinct molecules, no occurs. These properties make suitable candidates photocell applications.