P 4 S 3 and P,P′ or N,N′ Donors as Competitive Building Blocks in Copper(I) Coordination Polymers

The synthesis and characterization of hybrid polymers combining organic P,P′ (dppe) or N,N′ (pyrazine) ligands and inorganic donors (P 4 S 3 ) as cross‐linkers between copper(I) halide aggregates is described. As a simple model system the reaction of a mixture of P 4 S 3 , PEt 3 , and CuX (X = Cl, Br, I) was studied. According to X‐ray diffraction analysis, pseudotetrahedral monomers [CuX(PEt 3 ) 2 (P 4 S 3 )] ( 1 – 3 ) were formed, in which P 4 S 3 coordinates through the apical phosphorus atom. Layering a mixture of P 4 S 3 , Ph 2 PCH 2 CH 2 PPh 2 (dppe), and toluene with CuCl in MeCN under diffusion conditions gives 1D‐[CuCl(dppe)(MeCN)] ( 6 ), which contains (Cu 2 Cl 2 ) 2 (μ‐dppe) 2 clusters linked by another dppe ligand. The analogous reaction with CuI gives 1D‐[CuI(P 4 S 3 )(dppe)] ( 7 ), which is built up of alternating trans ‐(Cu 2 I 2 )(P 4 S 3 ) 2 units and dppe linkers. Hybrid polymers 2D‐[CuX(P 4 S 3 )(dppe)] [X = Br ( 8 ), I ( 9 )] are formed if CH 2 Cl 2 is used instead of toluene. The 2D structures of 8 and 9 may be derived from that of 7 by connecting neighboring (CuX)(dppe) strands with pairs of inversely coordinated P 4 S 3 cages. Replacement of dppe by pyrazine (pyz) yields 3D‐[(CuCl) 4 (P 4 S 3 ) 2 (pyz)] ( 10 ) and 3D‐[(CuBr) 3 (P 4 S 3 )(pyz)] ( 12 ), respectively. The structure of 10 comprises a 3D network composed of alternating, linked 2D‐[(CuCl) 2 (P 4 S 3 )] and 2D‐[CuCl(pyz)] layers. The structure of 12 contains cradles built from opposing (CuBr) 6 rings and pairwise pyz and P 4 S 3 bridges. These cradles are organized into a 3D framework by condensation of the (CuBr) 6 rings, and the layers formed are linked by additional pyz molecules. The resulting voids are occupied by toluene molecules. The behavior of P 4 S 3 and P,P′ or N,N′ ligands as competitive building blocks is also expressed by the formation of binary P 4 S 3 /CuX or pyz/CuX polymers.