Spacer length-directed construction of two-dimensional [MoS3Cu3]-based coordination polymers from a precursor cluster [PPh4][Cp∗MoS3(CuNCS)3] (Cp∗ = η5-C5Me5) and 4-pyridyl-based ditopic ligands

Reactions of an organometallic precursor cluster [PPh4][Cp∗MoS3(CuSCN)3] (Cp∗ = η5-C5Me5) (1) with three ditopic ligands with different spacer lengths including 4,4′-bipyridine (4,4′-bipy), 1,2-bis(4-pyridyl)ethylene (bpee) and 1,2-bis(4-pyridyl)ethane (bpe) in DMF/MeCN gave rise to three unique [MoS3Cu3]-based coordination polymers {[Cp∗MoS3Cu3(4,4′-bipy)1.5(μ-SCN)(SCN)]·DMF·MeCN}n (2), {[Cp∗MoS3Cu3(bpee)1.5(μ-SCN)(SCN)]·0.5(bpee)·2(DMF)}n (3) and {[Cp∗MoS3Cu3(bpe)1.5(μ-SCN)(SCN)]·0.5(bpe)·0.25(DMF)}n (4), respectively. Compounds 2–4 were characterized by elemental analysis, IR, UV–Vis, 1H NMR and single-crystal X-ray crystallography. For 2, each [Cp∗MoS3Cu3] cluster core, serving as a unique seesaw-shaped four-connecting node, is interlinked by single SCN bridges, single and double 4,4′-bipy bridges to form a 2D (4,4) corrugated network. For 3 or 4, each [Cp∗MoS3Cu3] cluster core, acting as a uncommon piano-stool-shaped three-connecting node, is interconnected by double SCN bridges, single and double bpee (or bpe) bridges to yield a 2D (6,3) latticed network. These results provided an interesting insight into the spacer length-controlled assembly of [MoS3Cu3]-based coordination polymers.