Assembly of [(η⁵-C₅Me₅)MoS₃Cu₃]-Supported One-Dimensional Chains with Single, Double, Triple, and Quadruple Strands

Abstract

The construction of a new set of [(eta5-C5Me5)MoS3Cu3]-based supramolecular compounds with different one-dimensional (1D) arrays from two preformed clusters [PPh4][(eta5-C5Me5)MoS3(CuX)3] (X = Br (1a), NCS (1b)) with 1,2-bis(4-pyridyl)ethane (bpe) and 1,3-bis(4-pyridyl)propane (bpp) is presented. Reactions of 1a with bpe in different molar ratios afforded ([((eta5-C5Me5)MoS3Cu3) 2(mu-bpe)3.5Br4].MeCN) n (2), ([((eta5-C5Me5)MoS3Cu3)2(mu-bpe)3Br4].Sol)n (3a: Sol = DMSO.3MeCN; 3b: Sol = 2aniline.3MeCN), ([((eta5-C 5Me5)MoS3Cu3)2(mu-bpe)3(bpe)Br4].0.35DMF)n (4), and ([((eta5-C5Me5)MoS3Cu3)2(mu-bpe)2(mu-Br)(mu3-Br)Br2].DMF.MeCN)n (5). On the other hand, treatment of 1a or 1b with bpp produced [(eta5-C5Me5)MoS3Cu3(mu-bpp)(mu-Br)Br]n (6) and ([((eta5-C5Me5)MoS3Cu3)2(mu-bpp)3(mu-NCS)2(NCS)](NCS))n (7). Compounds 2-7 have been characterized by elemental analysis, UV-vis spectroscopy, IR spectroscopy, 1H NMR, and X-ray analysis. In 2, each [(eta5-C5Me5)MoS3Cu3] core serves as an angular two-connecting node to link other equivalent cores by single and double bpe bridges to form a 1D "Great Wall"-like chain. In 3a and 3b, the [(eta5-C5Me5)MoS3Cu3] cores are linked alternatively by single and double bpe bridges to give a 1D zigzag chain. In 4, six cluster cores (two as a two-connecting node and four as a three-connecting node) are connected by four single bpe and two double bpe bridges to form a cyclohexane-shaped repeating unit, which is further fused with other units to generate a 1D double-stranded chain. Compound 5 has a simple 1D zigzag chain consisting of the cluster cores linked by single bpe bridges. In 6, the cluster cores are linked by single bpp bridges to give a 1D helical chain, which further holds two symmetry-related chains through C-H...Br hydrogen-bonding interactions, thereby forming a 1D H-bonded triple-stranded chain. Compound 7 has a rare 1D quadruple chain, in which the [(eta5-C5Me5)MoS3Cu3] cores work as planar four- and five-connecting nodes to interconnect other equivalent cores through single bpp bridges and single and double thiocyanate bridges. In addition, the third-order nonlinear optical properties of 1a, 2, 3a, and 4-7 in aniline were also investigated by using the Z-scan technique with a 4.5 ns pulse laser at 532 nm.

Reactions of [Et4N][Tp*W(μ3‐S)(μ‐S)2­(CuSCN)2] with Nitrogen Donor Ligands: Syntheses, Structures, and Third‐Order Nonlinear Optical Properties

“…When compared with nanosecond and picosecond measurement values, femtosecond values are roughly 2–3 orders of magnitude lower 15. The γ values of 2 – 4 are comparable to those of other M/Cu/S clusters derived from [MS 4 ] 2– , [MOS 3 ] 2– , [Cp*MS 3 ] – , and [Tp*MS 3 ] – (M = Mo, W), such as [(Et 4 N) 2 {WS 4 Cu 4 (CN) 4 }] n (1.26 × 10 –29 esu),3e [MoS 4 Cu 4 (α‐MePy) 5 Br 2 ] · 2(α‐MePy) 0.5 (1.06 × 10 –30 esu),16a [( n Bu) 4 N] 2 [MoOS 3 (CuNCS) 3 ] (4.8 × 10 –29 esu),16b [WOS 3 Cu 3 (4‐MePy) 6 ](BF 4 ) (4.43 × 10 –31 esu),16c [WOS 3 Cu 2 (4‐ t BuPy) 2 ] 2 (4.8 × 10 –30 esu),16d{[(Cp*MoS 3 Cu 3 ) 2 (μ‐bpp) 3 (μ‐NCS) 2 (NCS)](NCS)} n [bpp = 1,3‐bis(4‐pyridyl)propane, 3.86 × 10 –29 esu],5g [Et 4 N] 2 [Tp*W(μ 3 ‐S) 3 (CuNCS) 3 (μ 3 ‐Br)] · 1.5aniline (3.6 × 10 –32 esu), and {[Et 4 N][Tp*W(μ 3 ‐S) 3 (Cu‐μ‐SCN) 3 (Cu‐μ 3 ‐NCS)]} n (4.6 × 10 –32 esu) 9b. It is noted that the γ values of 2 – 4 are 1.2–2.2‐times larger than that of 1 (2.9 × 10 –32 esu) 9b.…”

Structural and Magnetic Analysis of Retrosynthetically Designed Architectures Built from a Triply Bridged Heterometallic (CuL)2Co Node and Benzenedicarboxylates

“…The variations in the structures are due to the different orientation of the carboxylate group of the BDC linkers (Figure 4). For 2 , the triply bridged trinuclear nodes are inclined toward each other to be accommodated by the 120°‐angular dicarboxylate linkers, generating a 1D “great wall”‐like coordination chain along the crystallographic c ‐axis (Figure 4, top) 24. This assembly represents a rare case of heterometallic coordination polymers involving isophthalic acid 25.…”

Heterometallic transition metal clusters and cluster-supported coordination polymers derived from Tp- and Tp*-based Mo(W) sulfido precursors

“…The formation of the 1D chain of 48 and the 2D network of 47 is probably due to the entropic advantage of the former system coupled with the different rigidity of the ligands in adopting to the coordination environments of Cu [89]. Such an observation was also made in the substitution reaction of the Cp*-based precursor clusters [90]. The one-pot reaction of P1 with CuCN and bipy resulted in the formation of [Tp*WS 3 Cu 2 (CN)(bipy) 0.5 ] (49) [87].…”