Cuprous Halide Complexes of a Variable Length Ligand: Helices, Cluster Chains, and Nets Containing Large Solvated Channels

The variable-length azacrown ether bridging ligand <i>N</i>,<i>N</i>′-bis­(3-pyridyl-methyl)­diaza-18-crown-6 (<b>b3pmdc</b>) was reacted with cuprous iodide to give a range of new discrete and polymeric coordination compounds. Six structurally diverse Cu^I(<b>b3pmdc</b>) architectures were isolated, as well as a single oxidized Cu^II(<b>b3pmdc</b>) species. These include the helical one-dimensional (1D) chain [H₄<b>b3pmdc</b>]­[Cu₁₀I₁₄]·CHCl₃·2H₂O (<b>1</b>), the luminescent linear cluster chain [Cu₄I₆(H₂<b>b3pmdc</b>)] (<b>2</b>), the guest water containing network [Cu₄I₄(H<b>b3pmdc</b>)₂]­(1.5ClO₄)­(0.5I₃)·3.5H₂O·2.5MeOH (<b>3</b>), the luminescent cubane cluster chain [Cu₄I₄(<b>b3pmdc</b>)₂] (<b>4</b>), the three-dimensional (3D) net [Cu₉I₁₂(K<b>b3pmdc</b>)₃(H₂O)₄]·9MeOH (<b>5</b>), the dinuclear mixed halide [Cu₂Cl_3.4I_2.6(H₄<b>b3pmdc</b>)] (<b>6</b>), and the cupric 1D chain [CuCl₂(H₂<b>b3pmdc</b>)­(MeOH)₂]·2Cl·2MeCN (<b>7</b>). Manipulation of the ligand conformation was achieved by the addition of the alkali metal salt potassium and by varying the pH of the solution with a range of acids (HCl, HClO₄). In the case of <b>2</b> and <b>4</b>, green and yellow luminescent emission was observed, as a result of the varied metal environment

Cuprous Halide Complexes of a Variable Length Ligand: Helices, Cluster Chains, and Nets Containing Large Solvated Channels

The variable-length azacrown ether bridging ligand <i>N</i>,<i>N</i>′-bis­(3-pyridyl-methyl)­diaza-18-crown-6 (<b>b3pmdc</b>) was reacted with cuprous iodide to give a range of new discrete and polymeric coordination compounds. Six structurally diverse Cu^I(<b>b3pmdc</b>) architectures were isolated, as well as a single oxidized Cu^II(<b>b3pmdc</b>) species. These include the helical one-dimensional (1D) chain [H₄<b>b3pmdc</b>]­[Cu₁₀I₁₄]·CHCl₃·2H₂O (<b>1</b>), the luminescent linear cluster chain [Cu₄I₆(H₂<b>b3pmdc</b>)] (<b>2</b>), the guest water containing network [Cu₄I₄(H<b>b3pmdc</b>)₂]­(1.5ClO₄)­(0.5I₃)·3.5H₂O·2.5MeOH (<b>3</b>), the luminescent cubane cluster chain [Cu₄I₄(<b>b3pmdc</b>)₂] (<b>4</b>), the three-dimensional (3D) net [Cu₉I₁₂(K<b>b3pmdc</b>)₃(H₂O)₄]·9MeOH (<b>5</b>), the dinuclear mixed halide [Cu₂Cl_3.4I_2.6(H₄<b>b3pmdc</b>)] (<b>6</b>), and the cupric 1D chain [CuCl₂(H₂<b>b3pmdc</b>)­(MeOH)₂]·2Cl·2MeCN (<b>7</b>). Manipulation of the ligand conformation was achieved by the addition of the alkali metal salt potassium and by varying the pH of the solution with a range of acids (HCl, HClO₄). In the case of <b>2</b> and <b>4</b>, green and yellow luminescent emission was observed, as a result of the varied metal environment

Cuprous Halide Complexes of a Variable Length Ligand: Helices, Cluster Chains, and Nets Containing Large Solvated Channels

The variable-length azacrown ether bridging ligand <i>N</i>,<i>N</i>′-bis­(3-pyridyl-methyl)­diaza-18-crown-6 (<b>b3pmdc</b>) was reacted with cuprous iodide to give a range of new discrete and polymeric coordination compounds. Six structurally diverse Cu^I(<b>b3pmdc</b>) architectures were isolated, as well as a single oxidized Cu^II(<b>b3pmdc</b>) species. These include the helical one-dimensional (1D) chain [H₄<b>b3pmdc</b>]­[Cu₁₀I₁₄]·CHCl₃·2H₂O (<b>1</b>), the luminescent linear cluster chain [Cu₄I₆(H₂<b>b3pmdc</b>)] (<b>2</b>), the guest water containing network [Cu₄I₄(H<b>b3pmdc</b>)₂]­(1.5ClO₄)­(0.5I₃)·3.5H₂O·2.5MeOH (<b>3</b>), the luminescent cubane cluster chain [Cu₄I₄(<b>b3pmdc</b>)₂] (<b>4</b>), the three-dimensional (3D) net [Cu₉I₁₂(K<b>b3pmdc</b>)₃(H₂O)₄]·9MeOH (<b>5</b>), the dinuclear mixed halide [Cu₂Cl_3.4I_2.6(H₄<b>b3pmdc</b>)] (<b>6</b>), and the cupric 1D chain [CuCl₂(H₂<b>b3pmdc</b>)­(MeOH)₂]·2Cl·2MeCN (<b>7</b>). Manipulation of the ligand conformation was achieved by the addition of the alkali metal salt potassium and by varying the pH of the solution with a range of acids (HCl, HClO₄). In the case of <b>2</b> and <b>4</b>, green and yellow luminescent emission was observed, as a result of the varied metal environment

Cuprous Halide Complexes of a Variable Length Ligand: Helices, Cluster Chains, and Nets Containing Large Solvated Channels

The variable-length azacrown ether bridging ligand <i>N</i>,<i>N</i>′-bis­(3-pyridyl-methyl)­diaza-18-crown-6 (<b>b3pmdc</b>) was reacted with cuprous iodide to give a range of new discrete and polymeric coordination compounds. Six structurally diverse Cu^I(<b>b3pmdc</b>) architectures were isolated, as well as a single oxidized Cu^II(<b>b3pmdc</b>) species. These include the helical one-dimensional (1D) chain [H₄<b>b3pmdc</b>]­[Cu₁₀I₁₄]·CHCl₃·2H₂O (<b>1</b>), the luminescent linear cluster chain [Cu₄I₆(H₂<b>b3pmdc</b>)] (<b>2</b>), the guest water containing network [Cu₄I₄(H<b>b3pmdc</b>)₂]­(1.5ClO₄)­(0.5I₃)·3.5H₂O·2.5MeOH (<b>3</b>), the luminescent cubane cluster chain [Cu₄I₄(<b>b3pmdc</b>)₂] (<b>4</b>), the three-dimensional (3D) net [Cu₉I₁₂(K<b>b3pmdc</b>)₃(H₂O)₄]·9MeOH (<b>5</b>), the dinuclear mixed halide [Cu₂Cl_3.4I_2.6(H₄<b>b3pmdc</b>)] (<b>6</b>), and the cupric 1D chain [CuCl₂(H₂<b>b3pmdc</b>)­(MeOH)₂]·2Cl·2MeCN (<b>7</b>). Manipulation of the ligand conformation was achieved by the addition of the alkali metal salt potassium and by varying the pH of the solution with a range of acids (HCl, HClO₄). In the case of <b>2</b> and <b>4</b>, green and yellow luminescent emission was observed, as a result of the varied metal environment

Cuprous Halide Complexes of a Variable Length Ligand: Helices, Cluster Chains, and Nets Containing Large Solvated Channels

The variable-length azacrown ether bridging ligand <i>N</i>,<i>N</i>′-bis­(3-pyridyl-methyl)­diaza-18-crown-6 (<b>b3pmdc</b>) was reacted with cuprous iodide to give a range of new discrete and polymeric coordination compounds. Six structurally diverse Cu^I(<b>b3pmdc</b>) architectures were isolated, as well as a single oxidized Cu^II(<b>b3pmdc</b>) species. These include the helical one-dimensional (1D) chain [H₄<b>b3pmdc</b>]­[Cu₁₀I₁₄]·CHCl₃·2H₂O (<b>1</b>), the luminescent linear cluster chain [Cu₄I₆(H₂<b>b3pmdc</b>)] (<b>2</b>), the guest water containing network [Cu₄I₄(H<b>b3pmdc</b>)₂]­(1.5ClO₄)­(0.5I₃)·3.5H₂O·2.5MeOH (<b>3</b>), the luminescent cubane cluster chain [Cu₄I₄(<b>b3pmdc</b>)₂] (<b>4</b>), the three-dimensional (3D) net [Cu₉I₁₂(K<b>b3pmdc</b>)₃(H₂O)₄]·9MeOH (<b>5</b>), the dinuclear mixed halide [Cu₂Cl_3.4I_2.6(H₄<b>b3pmdc</b>)] (<b>6</b>), and the cupric 1D chain [CuCl₂(H₂<b>b3pmdc</b>)­(MeOH)₂]·2Cl·2MeCN (<b>7</b>). Manipulation of the ligand conformation was achieved by the addition of the alkali metal salt potassium and by varying the pH of the solution with a range of acids (HCl, HClO₄). In the case of <b>2</b> and <b>4</b>, green and yellow luminescent emission was observed, as a result of the varied metal environment

Cuprous Halide Complexes of a Variable Length Ligand: Helices, Cluster Chains, and Nets Containing Large Solvated Channels

The variable-length azacrown ether bridging ligand <i>N</i>,<i>N</i>′-bis­(3-pyridyl-methyl)­diaza-18-crown-6 (<b>b3pmdc</b>) was reacted with cuprous iodide to give a range of new discrete and polymeric coordination compounds. Six structurally diverse Cu^I(<b>b3pmdc</b>) architectures were isolated, as well as a single oxidized Cu^II(<b>b3pmdc</b>) species. These include the helical one-dimensional (1D) chain [H₄<b>b3pmdc</b>]­[Cu₁₀I₁₄]·CHCl₃·2H₂O (<b>1</b>), the luminescent linear cluster chain [Cu₄I₆(H₂<b>b3pmdc</b>)] (<b>2</b>), the guest water containing network [Cu₄I₄(H<b>b3pmdc</b>)₂]­(1.5ClO₄)­(0.5I₃)·3.5H₂O·2.5MeOH (<b>3</b>), the luminescent cubane cluster chain [Cu₄I₄(<b>b3pmdc</b>)₂] (<b>4</b>), the three-dimensional (3D) net [Cu₉I₁₂(K<b>b3pmdc</b>)₃(H₂O)₄]·9MeOH (<b>5</b>), the dinuclear mixed halide [Cu₂Cl_3.4I_2.6(H₄<b>b3pmdc</b>)] (<b>6</b>), and the cupric 1D chain [CuCl₂(H₂<b>b3pmdc</b>)­(MeOH)₂]·2Cl·2MeCN (<b>7</b>). Manipulation of the ligand conformation was achieved by the addition of the alkali metal salt potassium and by varying the pH of the solution with a range of acids (HCl, HClO₄). In the case of <b>2</b> and <b>4</b>, green and yellow luminescent emission was observed, as a result of the varied metal environment

Cuprous Halide Complexes of a Variable Length Ligand: Helices, Cluster Chains, and Nets Containing Large Solvated Channels

The variable-length azacrown ether bridging ligand <i>N</i>,<i>N</i>′-bis­(3-pyridyl-methyl)­diaza-18-crown-6 (<b>b3pmdc</b>) was reacted with cuprous iodide to give a range of new discrete and polymeric coordination compounds. Six structurally diverse Cu^I(<b>b3pmdc</b>) architectures were isolated, as well as a single oxidized Cu^II(<b>b3pmdc</b>) species. These include the helical one-dimensional (1D) chain [H₄<b>b3pmdc</b>]­[Cu₁₀I₁₄]·CHCl₃·2H₂O (<b>1</b>), the luminescent linear cluster chain [Cu₄I₆(H₂<b>b3pmdc</b>)] (<b>2</b>), the guest water containing network [Cu₄I₄(H<b>b3pmdc</b>)₂]­(1.5ClO₄)­(0.5I₃)·3.5H₂O·2.5MeOH (<b>3</b>), the luminescent cubane cluster chain [Cu₄I₄(<b>b3pmdc</b>)₂] (<b>4</b>), the three-dimensional (3D) net [Cu₉I₁₂(K<b>b3pmdc</b>)₃(H₂O)₄]·9MeOH (<b>5</b>), the dinuclear mixed halide [Cu₂Cl_3.4I_2.6(H₄<b>b3pmdc</b>)] (<b>6</b>), and the cupric 1D chain [CuCl₂(H₂<b>b3pmdc</b>)­(MeOH)₂]·2Cl·2MeCN (<b>7</b>). Manipulation of the ligand conformation was achieved by the addition of the alkali metal salt potassium and by varying the pH of the solution with a range of acids (HCl, HClO₄). In the case of <b>2</b> and <b>4</b>, green and yellow luminescent emission was observed, as a result of the varied metal environment

Two-Dimensional and Three-Dimensional Coordination Polymers of Hexakis(4-cyanophenyl)[3]radialene: The Role of Stoichiometry and Kinetics

Hexakis­(4-cyanophenyl)­[3]­radialene (<b>1</b>) is a hexadentate ligand that has previously been shown to form isomorphous honeycomb two-dimensional (2-D) coordination polymers {[Ag­(<b>1</b>)]­(X)·2­(CH₃NO₂)}_<i>n</i> (X = ClO₄, <b>2a</b>; X = PF₆, <b>2b</b>) upon reaction with AgClO₄ and AgPF₆. Within these coordination polymers, close contacts were observed between the anions and the electron-deficient [3]­radialene core. Here the synthesis and characterization of four new coordination polymers of <b>1</b> and copper­(I), {[Cu₂(<b>1</b>)₂]­(X)₂·Y­(CH₃NO₂)}_<i>n</i> (X = BF₄, Y = 20, <b>4a</b>; X = PF₆, Y = 14, <b>4b</b>) and {[Cu­(<b>1</b>)]­(X)·2­(CH₃NO₂)}_<i>n</i> (X = BF₄, <b>5a</b>; X = PF₆, <b>5b</b>), are reported, along with two further examples of the (6,3) network {[Ag­(<b>1</b>)]­(X)·2­(CH₃NO₂)}_<i>n</i> (X = BF₄, <b>2c</b>; X = SbF₆, <b>2d</b>), and an 8-fold interpenetrated (10,3)-b net formed from <b>1</b> and AgClO₄, {[Ag₃(<b>1</b>)]­(ClO₄)₃·CH₃NO₂}_<i>n</i> (<b>3</b>). Coordination polymers <b>2a</b>–<b>2d</b> were synthesized using low ratios of ligand to metal, 1:1 to 1:3, whereas other examples described herein (compounds <b>3</b>, <b>4</b>, and <b>5</b>) were obtained via the use of a considerably higher ligand-to-metal salt ratio, in the range of 1:6 to 1:18. Reaction of <b>1</b> with [Cu­(CH₃CN)₄]­BF₄ and [Cu­(CH₃CN)₄]­PF₆ gave isostructural coordination polymers. In each experiment, a three-dimensional (3-D) network with a (4.6²)­(4².6)­(4³.6⁶.8⁶) topology (<b>4a</b> and <b>4b</b>) formed first, while a honeycomb two-dimensional (2-D) coordination polymer, with a fully cross-linked bilayer (<b>5a</b> and <b>5b</b>) crystallized second. Unlike the case for the Ag­(I) coordination polymers, the rate of crystallization rather than the stoichiometry of the reactions dictated the structure of the final product for the Cu­(I) compounds. The presence of radialene–anion interactions within these coordination polymers is also discussed, with anion-π interactions being observed to be of lesser significance relative to weak C–H···anion hydrogen bonding

Modulating Porosity through Conformer-Dependent Hydrogen Bonding in Copper(II) Coordination Polymers

A new divergent ligand, <i>N</i>,<i>N</i>′-bis­(4-carboxyphenylmethylene)­ethane-1,2-diamine (<b>H</b>_<b>4</b><b>L1</b>), has been prepared in high yield and used to generate two copper­(II) coordination polymer materials, <i>poly-</i>[Cu­(<b>H</b>_<b>2</b><b>L1</b>)­(OH₂)]·H₂O (<b>1</b>) and <i>poly</i>-[Cu­(<b>H</b>_<b>2</b><b>L1</b>)­(OH₂)]·H₂O·DMF (<b>2</b>). Both networks possess (4,4) sheet topologies and have almost identical compositions and coordination modes. The only major difference between the compounds lies with the conformation of the chelating ethylenediamine cores; compound <b>1</b> adopts a <i>trans</i>-(<i>R</i>,<i>R</i>/<i>S</i>,<i>S</i>) conformation, while compound <b>2</b> exhibits a <i>cis</i>-(<i>R</i>,<i>S</i>) conformation. This seemingly small difference arising from variation in synthetic conditions influences the extended structures of each network through hydrogen bonding interactions, resulting in the formation of a close packed 2-fold 2D → 2D parallel interpenetrated network for <b>1</b>, while the extended, non-interpenetrated structure of <b>2</b> contains aligned one-dimensional solvent channels. After solvent exchange and evacuation, compound <b>2</b> was found to adsorb approximately 35 cm³(STP)/g of CO₂ at atmospheric pressure at 273 K, with a zero-loading enthalpy of adsorption of −33 kJ/mol, while adsorbing only minimal quantities of N₂. These findings are a rare example of conformer-dependent porosity in otherwise geometrically similar frameworks and highlight the importance of understanding weak and fluxional secondary interactions in framework and ligand design

Synthesis and Structure of New Lanthanoid Carbonate “Lanthaballs”

New insights into the synthesis of high-nuclearity polycarbonatolanthanoid complexes have been obtained from a detailed investigation of the preparative methods that initially yielded the so-called “lanthaballs” [Ln₁₃(ccnm)₆(CO₃)₁₄(H₂O)₆(phen)₁₈] Cl₃(CO₃)·25H₂O [<b>α-1Ln</b>; Ln = La, Ce, Pr; phen = 1,10-phenanthroline; ccnm = carbamoylcyanonitrosomethanide]. From this investigation, we have isolated a new pseudopolymorph of the cerium analogue of the lanthaball, [Ce₁₃(ccnm)₆(CO₃)₁₄(H₂O)₆(phen)₁₈]·Cl₃·CO₃ (<b>β-1Ce</b>). This new pseudopolymorph arose from a preparation in which fixation of atmospheric carbon dioxide generated the carbonate, and the ccnm ligand was formed in situ by the nucleophilic addition of water to dicyanonitrosomethanide. From a reaction of cerium­(III) nitrate, instead of the previously used chloride salt, with (Et₄N)­(ccnm), phen, and NaHCO₃ in aqueous methanol, the new complex Na­[Ce₁₃(ccnm)₆(CO₃)₁₄(H₂O)₆(phen)₁₈]­(NO₃)₆·20H₂O (<b>2Ce</b>) crystallized. A variant of this reaction in which sodium carbonate was initially added to Ce­(NO₃)₃, followed by phen and (Et₄N)­(ccnm), also gave <b>2Ce</b>. However, an analogous preparation with (Me₄N)­(ccnm) gave a mixture of crystals of <b>2Ce</b> and the coordination polymer [CeNa­(ccnm)₄(phen)₃]·MeOH (<b>3</b>), which were manually separated. The use of cerium­(III) acetate in place of cerium nitrate in the initial preparation did not give a high-nuclearity complex but a new coordination polymer, [Ce­(ccnm)­(OAc)₂(phen)] (<b>4</b>). The first lanthaball to incorporate neodymium, namely, [Nd₁₃(ccnm)₄(CO₃)₁₄(NO₃)₄(H₂O)₇(phen)₁₅]­(NO₃)₃·10H₂O (<b>5Nd</b>), was isolated from a preparation similar to that of the second method used for <b>2Ce</b>, and its magnetic properties showed an antiferromagnetic interaction. The identity of all products was established by X-ray crystallography