New mixed metal complexes [PdTl(C boolean AND N)(CN)(2)] [C boolean AND N = 7,8-benzoquinolinate (bzq, 3); 2-phenylpyridinate (ppy, 4)] have been synthesized by reaction of their corresponding precursors (NBu4)[Pd(C boolean AND N)(CN)(2)] [C boolean AND N = bzq (1), ppy (2)] with TlPF6. Compounds 3 and 4 were studied by X-ray diffraction, showing the not-so-common Pd-II-Tl-I bonds. Both crystal structures exhibit 2-D extended networks fashioned by organometallic "PdTl(C boolean AND N)(CN)(2)" units, each one containing a donor acceptor Pd(II)-Tl(I) bond, which are connected through additional Tl center dot center dot center dot N C contacts and weak Tl center dot center dot center dot pi (bzq) contacts in the case of 3. Solid state emissions are red-shifted compared with those of the precursors and have been assigned to metal-metal'-to-ligand charge transfer (MM'LCT [d/s sigma*(Pd,Tl) -> pi*(C boolean AND N)]) mixed with some intraligand ((IL)-I-3[pi(C boolean AND N) -> pi*(C boolean AND N)]) character. In diluted solution either at room temperature or 77 K, the Pd-Tl bond is no longer retained as confirmed by mass spectrometry, NMR, and UV-vis spectroscopic techniques.