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 [(η⁵-C₅Me₅)MoS₃Cu₃]-supported supramolecular compounds from a preformed cluster [PPh₄][(η⁵-C₅Me₅)MoS₃(CuNCS)₃]·DMF (1·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 {[{(η⁵-C₅Me₅)MoS₃Cu₃}₂(NCS)₃(μ-NCS)(bpe)₃]·3aniline}_n (2) and [(η⁵-C₅Me₅)MoS₃Cu₃(1,4-pyz)(μ-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 (H₂tpyp) (D_4h symmetry if 21H and 23H of the H₂tpyp are omitted) at 100 °C for 12 h followed by extraction with aniline yielded another two polymeric clusters {[(η⁵-C₅Me₅)MoS₃Cu₃(tpt)(aniline)(NCS)₂]·0.75aniline· 0.5H₂O}_n (4) and {[(η⁵-C₅Me₅)MoS₃Cu₃(NCS)(μ-NCS)(H₂tpyp)_0.4(Cu−tpyp)_0.1]·2aniline·2.5benzene}_n (5). These compounds were characterized by elemental analysis, IR spectra, UV−vis spectra, ¹H NMR, and X-ray analysis. Compound 2 consists of a 2D (6,3) network in which [(η⁵-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 μ-NCS bridges. Compound 3 has a 3D diamondlike framework in which each [(η⁵-C₅Me₅)MoS₃Cu₃] core, acting as a tetrahedral connecting node, links four other neighboring units by 1,4-pyz bridges and μ-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 (4,6²)_core(4²,6²)_ligand network in which each cluster core acts as a T-shaped three-connecting node to link with other equivalent ones through μ-NCS bridges and H₂tpyp (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.