Construction of [(η5-C5Me5)MoS3Cu3]-based supramolecular assemblies from the [(η5-C5Me5)MoS3(CuNCS)3]- cluster anion and multitopic ligands with different symmetries

The assembly of a new family of [(eta(5)-C5Me5)MoS3Cu3]-supported supramolecular compounds from a preformed cluster [PPh4][(eta(5)-C5Me5)MoS3(CuNCS)(3)]center dot DMF (1 center dot DMF) with four multitopic ligands with different symmetries is described. Reactions of 1 with 1,2-bis(4-pyridyl)ethane (bpe) (C-s symmetry) or 1,4-pyrazine (1,4-pyz) (D-2h symmetry) in aniline gave rise to two polymeric clusters {[{(eta(5)-C5Me5)MoS3Cu3}(2)(NCS)(3)(mu-NCS)(bpe)(3)]center dot 3aniline}(n) (2) and [(eta(5)-C5Me5)MoS3Cu3(1,4-pyz)(mu-NCS)(2)](n) (3). On the other hand, solid-state reactions of 1 with 2,4,6-tri(4-pyridyl)-1,3,5-triazine (tpt) (D-3h symmetry) or 5,10,15,20-tetra(4-pyridyl)-21H,23H-porphyrin (H(2)tpyp) (D-4h symmetry if 21H and 23H of the H(2)tpyp are omitted) at 100 degrees C for 12 h followed by extraction with aniline yielded another two polymeric clusters {[(eta(5)-C5Me5)MoS3Cu3(tpt)(aniline)(NCS)(2)]center dot 0.75aniline center dot 0.5H(2)O}(n) (4) and {[(eta(5)-C5Me5)MoS3Cu3(NCS)(mu-NCS)(H(2)tpyp)(0).(4)(Cu-tpyp)(0).(1)]center dot 2aniline center dot 2.5benzene}(n) (5). These compounds were characterized by elemental analysis, IR spectra, UV-vis spectra, H-1 NMR, and X-ray analysis. Compound 2 consists of a 2D (6,3) network in which [(eta(5)-C5Me5)MoS3Cu3] cores serve both a T-shaped three-connecting node and an angular two-connecting node to interconnect other equivalent units through single bpe bridges, double bpe bridges, and mu-NCS bridges. Compound 3 has a 3D diamondlike framework in which each [(eta(5)-C5Me5)MoS3Cu3] core, acting as a tetrahedral connecting node, links four other neighboring units by 1,4-pyz bridges and mu-NCS bridges. Compound 4 contains a honeycomb 2D (6,3)(core)(6,3)(tpt) network in which each cluster core, serving a trigonal-planar three-connecting node, links three pairs of equivalent cluster cores via three tpt lignads. Compound 5 has a rare scalelike 2D (4,6(2))(core)(4(2),6(2))(ligand) network in which each cluster core acts as a T-shaped three-connecting node to link with other equivalent ones through mu-NCS bridges and H(2)tpyp (or Cu-tpyp) ligands. The results showed that the formation of the four different multidimensional topological structures was evidently affected by the symmetry of the ligands used. In addition, the third-order nonlinear optical properties of 1-5 in aniline were also investigated by using Z-scan techniques at 532 nm.