Design of Silver(I)-PTA Coordination Polymers through Controlled N,P-Coordination of 1,3,5-Triaza-7-phosphaadamantane (PTA) with Arylcarboxylates

Self-assembly reactions of silver(I) nitrate with 1,3,5-triaza-7-phosphaadamantane (PTA) as a main ligand and linker, and various benzenecarboxylic acids [benzoic (Hba), 4-cyanobenzoic (Hcba), 2-aminobenzoic (Haba), or terephthalic (H(2)tpa) acid] as ancillary ligand sources, provide the first general synthetic entry toward the controlled N,P-coordination mode of PTA, giving rise to the new series of coordination polymers [Ag(ba)(mu-PTA)](n) (1), [Ag(mu-cba)(mu-PTA)](n) 5nH(2)O (2), [Ag(mu-aba)(mu-PTA)](n) 3nH(2)O (3), and [Ag-2(mu(4)-tpa)(mu-PTA)(2)](n) 2nH(2)O (4) They have been isolated as air- and light-stable crystalline solids, characterized by IR and NMR spectroscopes, and elemental and single crystal X-ray diffraction analyses, which feature the generation of infinite PTA-driven ID or 2D metal-organic networks composed of various Ag-benzenecarboxylate nodes and PTA linkers A crucial synthetic and architectural defining role is played by the ancillary benzene-carboxylate ligand, a slight modification of which allows design of topologically distinct coordination networks that vary from ID zigzag (in 1), ladder-like (in 2), and tubular-like (in 3) chains to 2D gridlike undulating nets (in 4) Weak agostic interactions are observed between the C H groups of the ancillary ligands (in 1) or the methylene groups of PTA (in 2 and 4) and the silver(I) center The metal organic chains of 2 and 3 also act as host matrices for intercalated guest water molecules which are associated by multiple H-bonds into infinite 2D {(H2O)(11)}(n) wavelike layers (in 2) or discrete (H2O)(3) clusters (in 3), resulting also in further extension of silver-organic; hosts to 3D supramolecular frameworks Compounds 1-4 widen the very limited family of PTA-driven coordination polymers, representing also the first heteroligand coordination compounds that simultaneously bear PTA and carboxylate ligands