Four [Cu2I2]- or [Cu4I4]-based coordination polymers, [CuI(bpp)]n (1), {[Cu3I3(bpp)3]·2aniline·MeCN}n (2), {[Cu2I2(bpp)2]·2aniline}n (3), and [Cu4I4(bpp)2]n (4), were prepared by solvothermal reactions of CuI or Cu2(OH)2CO3 with 1,3-bis(4-pyridyl)propane (bpp) in different solvent systems. The preparation of 2 or 3 is involved in the in situ formation of aniline molecules and the reduction of Cu(II) to Cu(I). These compounds were characterized by elemental analysis, IR, and single crystal X-ray diffraction. Compound 1 consists of [Cu2I2] dimeric cores that link the neighboring ones via bpp bridges to form a one-dimensional double-bridged polymeric chain. Compound 2 or 3 has a similar chain structure in which the shape and size of the [Cu2I2(bpp)2]2 cavities that are occupied by MeCN/aniline or aniline solvent molecules are different from those of 1. Compound 4 has an intriguing two-dimensional 4-fold interpenetrated network in which each cubanelike [Cu4I4] core acts as a rare “seesaw”-shaped four-connecti...

Solvent Effects on the Assembly of [Cu2I2]- or [Cu4I4]-Based Coordination Polymers: Isolation, Structures, and Luminescent Properties

The investigation of heterometallic Mo(W)-M'-S clusters (M' = transition metals) has its genesis in the late 1970s with the identification of the nitrogenase iron-molybdenum cofactor (FeMoco) featuring a Mo-Fe-S double-cubane cluster core. This has led to the generation of a library of cluster skeletons subsequently used as building blocks for oligomers (OGs) and polymers, merging this field with the fascinating developments in supramolecular chemistry and coordination polymers (CPs). While resembling the general metal-ligand assembly to form CPs in one-pot, cluster-based OGs or CPs are conventionally prepared from Mo(W)-S synthons and Cu(i) salts in the presence of bridging ligands. This review summarizes the synthesis of Mo(W)-Cu-S cluster-supported OGs and CPs through a two-step strategy involving preformed clusters. This stepwise approach facilitates clean conversion, and is amenable to exquisite design protocols and yields products otherwise inaccessible via a direct one-pot method. We review the synthesis of OGs and CPs by cluster core upgrading, downgrading, ligand substitution, and cluster aggregation reactions, together with the optical and host-guest properties of the products. In doing so, we demonstrate the power and generality of this strategy for assembling these unique materials and offer clues on how to adapt this less practiced method to preparing extended molecular assemblies with potentially intriguing properties.

Rational construction of functional molybdenum (tungsten)–copper–sulfur coordination oligomers and polymers from preformed cluster precursors

Reaction of a cluster precursor [Et4N]2[MoOS3(CuCN)] (1) with equimolar [Cu(MeCN)4](PF6) in MeCN/aniline gave rise to an interesting polymeric cluster {[Et4N]2[MoOS3Cu2(μ-CN)]2·2aniline}n (2), whil...

Binuclear Cluster-to-Cluster-Based Supramolecular Compounds: Design, Assembly, and Enhanced Third-Order Nonlinear Optical Performances of {[Et4N]2[MoOS3Cu2(μ-CN)]2·2aniline}n and {[Et4N]4[MoOS3Cu3CN(μ′-CN)]2(μ-CN)2}n

Three new heterothiometallic cluster polymers with fascinating topologies have been synthesized by the self-assembly of preformed heterothiometallic cluster monomers and appropriate ligands Reaction of the monomeric cubic-shaped cluster [Et4N]3[MoOS3Cu3I4] with the D2h symmetry rigid bidentate 4,4′-bipy (4,4′-bipyridine) gave a two-dimensional (2D) layer compound [Mo2O2S6Cu6I2(4,4′-bipy)3(H2O)]n (1); the assembly of pentanuclear cluster monomer [Et4N]4[WS4Cu4I6] with Cs-symmetrical bpe (1,2-bis(4-pyridyl)ethane) afforded a 2D layer compound [WS4Cu4I2(bpe)3(H2O)]n (2), and the assembly of heptanuclear cluster monomer [Et4N]4[WS4Cu6I8] with D3h symmetry trigonal planar ligand timtz (2, 4, 6-tri(1H-imidazol-1-yl)-1, 3, 5-triazine) afforded a three-dimensional (3D) compound [WS4Cu6I4(timtz)8/3(H2O)12]n (3) X-ray crystallographic analysis reveals that 1 crystallizes in trigonal space group R3c with 2D 36-hxl net which is the first heterothiometallic superamolecular structure based on a twin cubic-shaped clu

Three new heterothiometallic cluster polymers with fascinating topologies.

The construction of a new set of [(η5-C5Me5)MoS3Cu3]-based supramolecular compounds with different one-dimensional (1D) arrays from two preformed clusters [PPh4][(η5-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 {[{(η5-C5Me5)MoS3Cu3}2(μ-bpe)3.5Br4]·MeCN}n (2), {[{(η5-C5Me5)MoS3Cu3}2(μ-bpe)3Br4]·Sol}n (3a: Sol = DMSO·3MeCN; 3b: Sol = 2aniline·3MeCN), {[{(η5-C5Me5)MoS3Cu3}2(μ-bpe)3(bpe)Br4]·0.35DMF}n (4), and {[{(η5-C5Me5)MoS3Cu3}2(μ-bpe)2(μ-Br)(μ3-Br)Br2]·DMF·MeCN}n (5). On the other hand, treatment of 1a or 1b with bpp produced [(η5-C5Me5)MoS3Cu3(μ-bpp)(μ-Br)Br]n (6) and {[{(η5-C5Me5)MoS3Cu3}2(μ-bpp)3(μ-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 [(η5-C5Me5)MoS3Cu3] core serves as an angular two-connecting node to link other equivalent cores by singl...

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

In our working toward the rational design and synthesis of cluster-based suppramolecular architectures, a set of new [WS4Cu4]- or [MoOS3Cu3]-based supramolecular assemblies have been prepared from reactions of preformed cluster compounds [Et4N]4[WS4Cu4I6] (1) and [(n-Bu)4N]2[MoOS3Cu3X3] (2, X = I; 3, X = SCN) with flexible ditopic ligands such as dipyridylsulfide (dps), dipyridyl disulfide (dpds), and their combinations with dicyanamide (dca) anion and 4,4‘-bipy. The cluster precursor 1 reacted with dps or dpds and sodium dicyanamide (dca) in MeCN to produce [WS4Cu4I2(dps)3]·2MeCN (4·2MeCN) and [WS4Cu4(dca)2(dpds)2]·Et2O·2MeCN (5·Et2O·2MeCN), respectively. On the other hand, treatment of 2 with dpds in DMF/MeCN afforded [MoOS3Cu3I(dpds)2]·0.5DMF·2(MeCN)0.5 (6·0.5DMF·2(MeCN)0.5) while reaction of 3 with sodium dicyanamide (dca) and 4,4‘-bipy in DMF/MeCN gave rise to [MoOS3Cu3(dca)(4,4‘-bipy)1.5]·DMF·MeCN (7·DMF·MeCN). Compounds 4·2MeCN, 5·Et2O·2MeCN, 6·0.5DMF·2(MeCN)0.5, and 7·DMF·MeCN have been characteri...

Mo(W)/Cu/S cluster-based supramolecular arrays assembled from preformed clusters [Et4N]4[WS4Cu4I6] and [(n-Bu)4N]2[MoOS3Cu3X3] (X = I, SCN) with flexible ditopic ligands.

An asymmetric bis(dithienylethene-acetylide) ruthenium(II) complex trans-Ru(dppe)2(L1o)(L2o) (1oo) incorporating two different dithienylethene–acetylides (L1o and L2o) was designed to modulate multistate photochromism in view of the well separated ring-closing absorption bands between L1o and L2o. Upon irradiation with appropriate wavelengths of light, complex 1 undergoes stepwise photocyclization and selective photocycloreversion to afford four states (1oo, 1co, 1oc, and 1cc). As a contrast, symmetric complexes trans-Ru(dppe)2(L1o)2 (2oo) and trans-Ru(dppe)2(L2o)2 (3oo) with two identical dithienylethene-acetylides were synthesized, and the corresponding photochromic behavior was investigated. The photochromic properties of the oxidized species (1oo+/1co+/1oc+/1cc+, 2oo+/2co+/2cc+, and 3oo+/3co+/3cc+) were also investigated. The ring-closing absorption bands of one-electron oxidized species 1oo+, 2oo+, and 3oo+ show obvious blue shifts relative to those of 1oo, 2oo, and 3oo, respectively. The ring-closin...

Multiphotochromism in an Asymmetric Ruthenium Complex with Two Different Dithienylethenes.

4,5-Bis(2-methyl-5-phenylthiophen-3-yl)-1,3-dithiol-2-one (L1o) was elaborately designed to afford dithienyl-dithiolene as a new photochromic ligand. We describe herein the preparation and characterization of unprecedented photochromic dithienyl-dithiolene complexes with cis-orientation of dithienylethene (DTE) stabilized by metal chelation instead of conventional cyclopentene. The treatment of L1o with sodium methoxide in methanol afforded a disodium salt of dithiolate dianion, which reacts with M(dppe)Cl2 (dppe = 1,2-bis(diphenylphosphino)ethane, M = Ni, Pd) to give neutral compounds M(dppe)(dithiolate) as established by X-ray crystallography. The reaction of L1o with NiCl2 in the presence of sodium methoxide allows the isolation of an anionic nickel(II) bis(dithienyl-dithiolene) complex with photochemical inertness. In contrast, the corresponding reaction with ZnCl2 afforded a dianionic zinc(II) complex chelated by two dianionic dithienyl-dithiolenes, which displays stepwise photocyclization upon irradiation with UV light at 312 nm as demonstrated experimentally and theoretically. Only when dithienyl-dithiolene behaves as a dicationic ligand instead of neutral or monoanionic species, it is possible to achieve reversible photochromism in the corresponding metal complexes.

An unprecedented photochromic system with cis-oriented dithienyl-dithiolenes supported by metal chelation

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Mo(W)/Cu/S cluster-based supramolecular arrays assembled from preformed clusters [Et4N]4[WS4Cu4I6] and [(n-Bu)4N]2[MoOS3Cu3X3] (X = I, SCN) with flexible ditopic ligands.

Multiphotochromism in an Asymmetric Ruthenium Complex with Two Different Dithienylethenes.

An unprecedented photochromic system with cis-oriented dithienyl-dithiolenes supported by metal chelation