Reaction of the complex [Cp2Cr2(CO)(4)(mu,eta(2)-P2)] (2) with copper(I) halides leads to the quantitative formation of the new one-dimensional (1D) linear polymers [CuX{Cp2Cr2(CO)(4)-(mu,eta(2):eta(1):eta(1)-P-2)}](n) [X = Cl (3), Br (4), I (5)]. Polymers 3-5 are the first examples of supramolecular aggregates incorporating 2 as a connecting moiety. The solid-state structures of 3-5 are compared and their remarkable influence on the respective solid-state P-31 magic angle spinning (MAS) NMR spectra is interpreted with the help of density functional theory (DFT) calculations, which suggest that the P-31 chemical shifts are extremely sensitive to the position of the phosphorus atoms with respect to the cones of anisotropy of the carbonyl ligands. (c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007.