ABSTRACT: This work demonstrates that PTA (1,3,5-triaza-7-phosphaadamantane) behaves as an orthogonal ligand between Ru(II) and Zn(II), since it selectively binds through the P atom to ruthenium and through one or more of the N atoms to zinc. This property of PTA was exploited for preparing the two monomeric porphyrin adducts with axially bound PTA, [Ru(TPP)(PTA-κP)2] (1, TPP = meso-tetraphenylporphyrin) and [Zn(TPP)(PTA-κN)] (3). Next, we prepared a number of heterobimetallic Ru/Zn porphyrin polymeric networks-and two discrete molecular systems-mediated by P,N-bridging PTA in which either both metals reside inside a porphyrin core, or one metal belongs to a porphyrin, either Ru(TPP) or Zn(TPP), and the other to a complex or salt of the complementary metal (i.e., cis,cis,trans-[RuCl2(CO)2(PTA-κP)2] (5), trans-[RuCl2(PTA-κP)4] (7), Zn(CH3COO)2, and ZnCl2). The molecular compounds 1, 3, trans-[{RuCl2(PTA-κ2P,N)4}{Zn(TPP)}4] (8), and [{Ru(TPP)(PTA-κP)(PTA-κ2P,N)}{ZnCl2(OH2)}] (11), as well as the polymeric species [{Ru(TPP)(PTA-κ2P,N)2}{Zn(TPP)}]∞ (4), cis,cis,trans-[{RuCl2(CO)2(PTA-κ2P,N)2}{Zn(TPP)}]∞ (6), trans-[{RuCl2(PTA-κ2P,N)4}{Zn(TPP)}2]∞ (9), and [{Ru(TPP)(PTA-κ3P,2N)2}{Zn9(CH3COO)16(CH3OH)2(OH)2}]∞ (10), were structurally characterized by single crystal X-ray diffraction. Compounds 4, 6, 9, and 10 are the first examples of solid-state porphyrin networks mediated by PTA. In 4, 6, 8, 9, and 11 the bridging PTA has the κ2P,N binding mode, whereas in the 2D polymeric layers of 10 it has the triple-bridging mode κ3P,2N. The large number of compounds with the six-coordinate Zn(TPP) (the three polymeric networks of 4, 6 and 9, out of five compounds) strongly suggests that the stereoelectronic features of PTA are particularly well-suited for this relatively rare type of coordination. Interestingly, the similar 1D polymeric chains 4 and 6 have different shapes (zigzag in 4 vs "Greek frame" in 6) because the {trans-Ru(PTA-κ2P,N)2} fragment bridges two Zn(TPP) units with anti geometry in 4 and with syn geometry in 6. Orthogonal "Greek frame" 1D chains make the polymeric network of 9. Having firmly established the binding preferences of PTA toward Ru(II) and Zn(II), we are confident that in the future a variety of Ru/Zn solid-state networks can be produced by changing the nature of the partners. In particular, there are several inert Ru(II) compounds that feature two or more P-bonded PTA ligands that might be exploited as connectors of well-defined geometry for the rational design of solid-state networks with Zn-porphyrins (or other Zn compounds).
