The complexes [Pd(L)(CH3CN)][BF4] (L(3) = 5,8,11-trioxa-2,14-dithia[15]-m-cyclophane and L(5) = 5,8,11,14,17-pentaoxa-2,20-dithia[21]-m-cyclophane) were prepared by palladation of the respective thiacyclophane employing [Pd(CH3CN)(4)][BF4](2) These metalloreceptors were reacted with various small substrates (H2O, NH3, NH(2)R, NMR(2) NH2NH2, and NH2NH3+) capable of simultaneously coordinating to the Pd center and hydrogen-bonding with the peripheral ether oxygens. [Pd(L(3))(NH3)][BF4] crystallized in the space group Pbca with a = 21.377(4) Angstrom, b = 21.656(5) Angstrom, c = 9.437(6) Angstrom, V = 4368(2) Angstrom(3), and Z = 8. The structure refined to R = 6.41% and R(w) = 7.03% for 659 reflections with F-o(2) > 3 sigma(F-o(2)). [Pd(L(3))(NH2NH2)][BF4] crystallized in the space group P ($) over bar 1 with a = 11.652(3> Angstrom, b = 12.669(4) Angstrom, c = 8.355(1) Angstrom, a = 94.13(2)degrees, beta = 94.34(2)degrees, gamma = 117.21(1)degrees, V = 1090.3(5) Angstrom(3), and Z = 2. The structure refined to R = 2.81% and R(w) = 3.40% for 2709 reflections with F-o(2) > 3 sigma(F-o(2)). [Pd(L(5))(H2O)][BF4] crystallized in the space group P1 ($) over bar with a = 11.076(3) Angstrom, b = 15.147(5) Angstrom, c = 8.586(2) Angstrom, V = 1284(1) Angstrom(3), and Z = 2. The structure refined to R = 3.14% and R(w) = s with F-o(2) > 3 sigma(F-o(2)). [Pd(L(3))(NH2NH3)][CF3SO3](2) crystallized in the space group P2(1)/c with a = 11.906(4) Angstrom, b = 17.19(1) Angstrom, c = 15.313(4) Angstrom beta = 111.18(2)degrees, V = 2923(4) Angstrom(3), and Z = 4.