A Giant Polyaluminum Species S−Al₃₂ and Two Aluminum Polyoxocations Involving Coordination by Sulfate Ions S−Al₃₂ and S−K−Al₁₃

The giant polyaluminum species [Al32O8(OH)60(H2O)28(SO4)2]16+ (S−Al32) and [Al13O4(OH)25(H2O)10(SO4)]4+ (S−K−Al13) [S means that sulfate ions take part in coordination of the aluminum polycation; K represents the Keggin structure] were obtained in the structures of [Al32O8(OH)60(H2O)28(SO4)2][SO4]7[Cl]2·30H2O and [Al13O4(OH)25(H2O)10(SO4)]4[SO4]8·20H2O, respectively. They are the first two aluminum polyoxocations coordinated by sulfate ions. The “core-shell” structure of S−Al32 is similar to that of Al30, but the units are linked by two [Al(OH)2(H2O)3(SO4)]− groups with replacement of four η1-H2O molecules. The structure of S−K−Al13 is similar to the well-known structure of ε-K−Al13, but the units are linked by two (SO42−)0.5 with replacement of a H3O+ ion. It was shown that strong interaction exists between the polyoxocations and counterions. On the basis of their structural features and preparation conditions, a formation and evolution mechanism (from ε-K−Al13 to S−K−Al13 and S−Al32) has been proposed. A local basification degree symmetrical equalization principle was extracted based on a comparison of the calculated results of the local basification degree for each central Al3+ ion included in a polycation. They can be used to explain how the two aluminum species are formed and evolved and why the sulfate ions can coordinate to them and to predict where the OH-bridging positions will be upon further hydrolysis

A Giant Polyaluminum Species S−Al₃₂ and Two Aluminum Polyoxocations Involving Coordination by Sulfate Ions S−Al₃₂ and S−K−Al₁₃

The giant polyaluminum species [Al32O8(OH)60(H2O)28(SO4)2]16+ (S−Al32) and [Al13O4(OH)25(H2O)10(SO4)]4+ (S−K−Al13) [S means that sulfate ions take part in coordination of the aluminum polycation; K represents the Keggin structure] were obtained in the structures of [Al32O8(OH)60(H2O)28(SO4)2][SO4]7[Cl]2·30H2O and [Al13O4(OH)25(H2O)10(SO4)]4[SO4]8·20H2O, respectively. They are the first two aluminum polyoxocations coordinated by sulfate ions. The “core-shell” structure of S−Al32 is similar to that of Al30, but the units are linked by two [Al(OH)2(H2O)3(SO4)]− groups with replacement of four η1-H2O molecules. The structure of S−K−Al13 is similar to the well-known structure of ε-K−Al13, but the units are linked by two (SO42−)0.5 with replacement of a H3O+ ion. It was shown that strong interaction exists between the polyoxocations and counterions. On the basis of their structural features and preparation conditions, a formation and evolution mechanism (from ε-K−Al13 to S−K−Al13 and S−Al32) has been proposed. A local basification degree symmetrical equalization principle was extracted based on a comparison of the calculated results of the local basification degree for each central Al3+ ion included in a polycation. They can be used to explain how the two aluminum species are formed and evolved and why the sulfate ions can coordinate to them and to predict where the OH-bridging positions will be upon further hydrolysis

A Giant Polyaluminum Species S−Al₃₂ and Two Aluminum Polyoxocations Involving Coordination by Sulfate Ions S−Al₃₂ and S−K−Al₁₃

The giant polyaluminum species [Al32O8(OH)60(H2O)28(SO4)2]16+ (S−Al32) and [Al13O4(OH)25(H2O)10(SO4)]4+ (S−K−Al13) [S means that sulfate ions take part in coordination of the aluminum polycation; K represents the Keggin structure] were obtained in the structures of [Al32O8(OH)60(H2O)28(SO4)2][SO4]7[Cl]2·30H2O and [Al13O4(OH)25(H2O)10(SO4)]4[SO4]8·20H2O, respectively. They are the first two aluminum polyoxocations coordinated by sulfate ions. The “core-shell” structure of S−Al32 is similar to that of Al30, but the units are linked by two [Al(OH)2(H2O)3(SO4)]− groups with replacement of four η1-H2O molecules. The structure of S−K−Al13 is similar to the well-known structure of ε-K−Al13, but the units are linked by two (SO42−)0.5 with replacement of a H3O+ ion. It was shown that strong interaction exists between the polyoxocations and counterions. On the basis of their structural features and preparation conditions, a formation and evolution mechanism (from ε-K−Al13 to S−K−Al13 and S−Al32) has been proposed. A local basification degree symmetrical equalization principle was extracted based on a comparison of the calculated results of the local basification degree for each central Al3+ ion included in a polycation. They can be used to explain how the two aluminum species are formed and evolved and why the sulfate ions can coordinate to them and to predict where the OH-bridging positions will be upon further hydrolysis

Crystal Structure of [Al₄(OH)₆(H₂O)₁₂][Al(H₂O)₆]₂Br₁₂: A New Polyaluminum Compound

A vertex-shared tetrahedral [Al4(OH)6(H2O)12]6+ (Al4) and a disordered [Al(H2O)6]3+ (Al1) that coexist in a 1:2 ratio within each unit cell were observed in the structure of [Al4(OH)6(H2O)12][Al(H2O)6]2Br12, which crystallized in a cubic Fd3̅m space group from a spontaneously hydrolyzed solution of AlBr3. The former is composed of four AlO6 octahedra that are connected to each other by sharing three vertexes of each octahedron and form a large regular tetrahedron with ideal Td symmetry. The central Al3+ ion of the latter is coordinated by 6 disordered OH2 molecules, that form a core–shell structure with ideal D3d symmetry

Crystal Structure of [Al₄(OH)₆(H₂O)₁₂][Al(H₂O)₆]₂Br₁₂: A New Polyaluminum Compound

A vertex-shared tetrahedral [Al4(OH)6(H2O)12]6+ (Al4) and a disordered [Al(H2O)6]3+ (Al1) that coexist in a 1:2 ratio within each unit cell were observed in the structure of [Al4(OH)6(H2O)12][Al(H2O)6]2Br12, which crystallized in a cubic Fd3̅m space group from a spontaneously hydrolyzed solution of AlBr3. The former is composed of four AlO6 octahedra that are connected to each other by sharing three vertexes of each octahedron and form a large regular tetrahedron with ideal Td symmetry. The central Al3+ ion of the latter is coordinated by 6 disordered OH2 molecules, that form a core–shell structure with ideal D3d symmetry

<b>Absolute Structures of a Mirror Pair of Infinite Na(H₂O)₄</b>⁺<b>‑Connected ε‑Keggin–Al₁₃ Species</b>

The absolute structures of a pair of infinite Na­(H2O)4+-connected ε-Keggin–Al13 species (Na−ε-K–Al13) that were inversion structures and mirror images of each other were determined. Single crystals obtained by adding A2SO4 (A = Li, Na, K, Rb, or Cs) solution to NaOH-hydrolyzed AlCl3 solution were subjected to X-ray structure analyses. The statistical results for 36 single crystals showed that all the crystals had almost the same unit cell parameter, belonged to the same F4̅3m space group, and possessed the same structural formula [Na­(H2O)4AlO4Al12(OH)24(H2O)12]­(SO4)4·10H2O. However, the crystals had two inverse absolute structures (denoted A and B), which had a crystallization ratio of 1:1. From Li+ to Cs+, with increasing volume of the cation coexisting in the mother solution, the degree of disorder of the four H2O molecules in the Na­(H2O)4+ hydrated ion continuously decreased; they became ordered when the cation was Cs+. Absolute structures A and B are the first two infinite aluminum polycations connected by statistically occupied [(Na1/4)4(H2O)4]+ hydrated ions. The three-dimensional structure of the infinite Na−ε-K–Al13 species can be regarded as the assembly of finite ε-K–Al13 species linked by [(Na1/4)4(H2O)4]+ in a 1:1 ratio. In this assembly, each [(Na1/4)4(H2O)4]+ is connected to four ε-K–Al13 and each ε-K–Al13 is also connected to four [(Na1/4)4(H2O)4]+ in tetrahedral orientations to form a continuous rigid framework structure, which has an inverse spatial orientation between absolute structure A and B. This discovery clarifies that the ε-K–Al13 (or ε-K–GaAl12) species in Na­[MO4Al12(OH)24(H2O)12]­(XO4)4·nH2O (M = Al, Ga; X = S, Se; n = 10–20) exists as discrete groups and deepens understanding of the formation and evolution process of polyaluminum species in forcibly hydrolyzed aluminum salt solution. The reason why Na+ statistically occupies the four sites was examined, and a formation and evolution mechanism of the infinite Na−ε-K–Al13 species was proposed

Cancer sp.

Hydrothermal reactions of aromatic 3,3′,5,5′-biphenyltetracarboxylic acid (H₄bpt) and the transitional metal cations in the presence of rigid or flexible N-donor ancillary ligands afford nine novel coordination polymers, namely, [M­(H₂bpt)­(Hpptp)]_<i>n</i> (M = Mn (<b>1</b>), Fe (<b>2</b>), Co (<b>3</b>), and Zn (<b>4</b>)), [Mn₂(bpt)­(Hpptp)₂]_<i>n</i> (<b>5</b>), {[Zn₃(Hbpt)­(bpt)­(H₂O)₂]­[(4,4′-H₂bmib)_0.5]·H₂O}_<i>n</i> (<b>6</b>), {[Cu­(bpt)_0.5(4,4′-bimbp)]·H₂O}_<i>n</i> (<b>7</b>), {[Co­(H₂bpt)­(2,7-dfo)]·H₂O}_<i>n</i> (<b>8</b>), and {[Ni₂(bpt)­(4,4′-bibp)_2.5(H₂O)]·3­(H₂O)}_<i>n</i> (<b>9</b>) (Hpptp = 2-(3-(4-(pyridin-4-yl)­phenyl)-1<i>H</i>-1,2,4-triazol-5-yl)­pyridine; 4,4′-bmib = 4,4′-bis­(2-methylimidazol-1-yl)­benzene; 4,4′-bimbp = 4,4′-bis­(imidazol-1-ylmethyl)­biphenyl; 2,7-dfo = 2,7-di­(imidazo-1-ly)-9<i>H</i>-fluoren-9-one; 4,4′-bibp = 4,4′-bis­(imidazol)­biphenyl). Their structures have been determined by single-crystal X-ray diffraction analyses, elemental analyses, IR spectra, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analyses. Complexes <b>1</b>–<b>4</b> are isomorphism and feature a similar 2-fold interpenetrating 2D helical double layer, which is further extended via the interlayer π···π interactions into a 3D supramolecular structure. Complex <b>5</b> displays a pillared-layer 3D porous network with a (6².8)₂(6².8².10²) topology. Compound <b>6</b> shows an unprecedented 3D host-framework consisting of Zn₆ clusters and exhibits a novel 3D (5,5,5,6,9)-connected topological net with the Schläfli symbol of (4¹⁰.6⁵)­(4¹⁹.6¹⁶.8)­(4⁶.6⁴)­(4⁷.6³)₂. The topology of <b>7</b> is an unprecedented binodal (4,4)-connected 3D network with the Schläfli symbol of (6².8⁴)­(4².8²)₂. Complex <b>8</b> exhibits a 3D (6⁶) structure with left- and right-handed helical chains arranged alternately. Complex <b>9</b> is a novel trinodal (4,4,5)-connected 3D framework with the Schläfli symbol of (6⁴.8²)­(6⁵.8)­(6⁸.8²). To the best of our knowledge, the 3D frameworks with (5,5,5,6,9)-connected net for <b>6</b>, binodal (4,4)-connected for <b>7</b>, and trinodal (4,4,5)-connected for <b>9</b> have never been documented to date. Moreover, the luminescent properties of <b>4</b> and <b>6</b> have been investigated

Syntheses, Structures, and Properties of a Series of Multidimensional Metal–Organic Polymers Based on 3,3′,5,5′-Biphenyltetracarboxylic Acid and N‑Donor Ancillary Ligands

Hydrothermal reactions of aromatic 3,3′,5,5′-biphenyltetracarboxylic acid (H4bpt) and the transitional metal cations in the presence of rigid or flexible N-donor ancillary ligands afford nine novel coordination polymers, namely, [M­(H2bpt)­(Hpptp)]n (M = Mn (1), Fe (2), Co (3), and Zn (4)), [Mn2(bpt)­(Hpptp)2]n (5), {[Zn3(Hbpt)­(bpt)­(H2O)2]­[(4,4′-H2bmib)0.5]·H2O}n (6), {[Cu­(bpt)0.5(4,4′-bimbp)]·H2O}n (7), {[Co­(H2bpt)­(2,7-dfo)]·H2O}n (8), and {[Ni2(bpt)­(4,4′-bibp)2.5(H2O)]·3­(H2O)}n (9) (Hpptp = 2-(3-(4-(pyridin-4-yl)­phenyl)-1H-1,2,4-triazol-5-yl)­pyridine; 4,4′-bmib = 4,4′-bis­(2-methylimidazol-1-yl)­benzene; 4,4′-bimbp = 4,4′-bis­(imidazol-1-ylmethyl)­biphenyl; 2,7-dfo = 2,7-di­(imidazo-1-ly)-9H-fluoren-9-one; 4,4′-bibp = 4,4′-bis­(imidazol)­biphenyl). Their structures have been determined by single-crystal X-ray diffraction analyses, elemental analyses, IR spectra, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analyses. Complexes 1–4 are isomorphism and feature a similar 2-fold interpenetrating 2D helical double layer, which is further extended via the interlayer π···π interactions into a 3D supramolecular structure. Complex 5 displays a pillared-layer 3D porous network with a (62.8)2(62.82.102) topology. Compound 6 shows an unprecedented 3D host-framework consisting of Zn6 clusters and exhibits a novel 3D (5,5,5,6,9)-connected topological net with the Schläfli symbol of (410.65)­(419.616.8)­(46.64)­(47.63)2. The topology of 7 is an unprecedented binodal (4,4)-connected 3D network with the Schläfli symbol of (62.84)­(42.82)2. Complex 8 exhibits a 3D (66) structure with left- and right-handed helical chains arranged alternately. Complex 9 is a novel trinodal (4,4,5)-connected 3D framework with the Schläfli symbol of (64.82)­(65.8)­(68.82). To the best of our knowledge, the 3D frameworks with (5,5,5,6,9)-connected net for 6, binodal (4,4)-connected for 7, and trinodal (4,4,5)-connected for 9 have never been documented to date. Moreover, the luminescent properties of 4 and 6 have been investigated

Syntheses, Structures, and Properties of a Series of Multidimensional Metal–Organic Polymers Based on 3,3′,5,5′-Biphenyltetracarboxylic Acid and N‑Donor Ancillary Ligands

Hydrothermal reactions of aromatic 3,3′,5,5′-biphenyltetracarboxylic acid (H₄bpt) and the transitional metal cations in the presence of rigid or flexible N-donor ancillary ligands afford nine novel coordination polymers, namely, [M­(H₂bpt)­(Hpptp)]_<i>n</i> (M = Mn (<b>1</b>), Fe (<b>2</b>), Co (<b>3</b>), and Zn (<b>4</b>)), [Mn₂(bpt)­(Hpptp)₂]_<i>n</i> (<b>5</b>), {[Zn₃(Hbpt)­(bpt)­(H₂O)₂]­[(4,4′-H₂bmib)_0.5]·H₂O}_<i>n</i> (<b>6</b>), {[Cu­(bpt)_0.5(4,4′-bimbp)]·H₂O}_<i>n</i> (<b>7</b>), {[Co­(H₂bpt)­(2,7-dfo)]·H₂O}_<i>n</i> (<b>8</b>), and {[Ni₂(bpt)­(4,4′-bibp)_2.5(H₂O)]·3­(H₂O)}_<i>n</i> (<b>9</b>) (Hpptp = 2-(3-(4-(pyridin-4-yl)­phenyl)-1<i>H</i>-1,2,4-triazol-5-yl)­pyridine; 4,4′-bmib = 4,4′-bis­(2-methylimidazol-1-yl)­benzene; 4,4′-bimbp = 4,4′-bis­(imidazol-1-ylmethyl)­biphenyl; 2,7-dfo = 2,7-di­(imidazo-1-ly)-9<i>H</i>-fluoren-9-one; 4,4′-bibp = 4,4′-bis­(imidazol)­biphenyl). Their structures have been determined by single-crystal X-ray diffraction analyses, elemental analyses, IR spectra, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analyses. Complexes <b>1</b>–<b>4</b> are isomorphism and feature a similar 2-fold interpenetrating 2D helical double layer, which is further extended via the interlayer π···π interactions into a 3D supramolecular structure. Complex <b>5</b> displays a pillared-layer 3D porous network with a (6².8)₂(6².8².10²) topology. Compound <b>6</b> shows an unprecedented 3D host-framework consisting of Zn₆ clusters and exhibits a novel 3D (5,5,5,6,9)-connected topological net with the Schläfli symbol of (4¹⁰.6⁵)­(4¹⁹.6¹⁶.8)­(4⁶.6⁴)­(4⁷.6³)₂. The topology of <b>7</b> is an unprecedented binodal (4,4)-connected 3D network with the Schläfli symbol of (6².8⁴)­(4².8²)₂. Complex <b>8</b> exhibits a 3D (6⁶) structure with left- and right-handed helical chains arranged alternately. Complex <b>9</b> is a novel trinodal (4,4,5)-connected 3D framework with the Schläfli symbol of (6⁴.8²)­(6⁵.8)­(6⁸.8²). To the best of our knowledge, the 3D frameworks with (5,5,5,6,9)-connected net for <b>6</b>, binodal (4,4)-connected for <b>7</b>, and trinodal (4,4,5)-connected for <b>9</b> have never been documented to date. Moreover, the luminescent properties of <b>4</b> and <b>6</b> have been investigated

Syntheses, Structures, and Properties of a Series of Multidimensional Metal–Organic Polymers Based on 3,3′,5,5′-Biphenyltetracarboxylic Acid and N‑Donor Ancillary Ligands

Hydrothermal reactions of aromatic 3,3′,5,5′-biphenyltetracarboxylic acid (H₄bpt) and the transitional metal cations in the presence of rigid or flexible N-donor ancillary ligands afford nine novel coordination polymers, namely, [M­(H₂bpt)­(Hpptp)]_<i>n</i> (M = Mn (<b>1</b>), Fe (<b>2</b>), Co (<b>3</b>), and Zn (<b>4</b>)), [Mn₂(bpt)­(Hpptp)₂]_<i>n</i> (<b>5</b>), {[Zn₃(Hbpt)­(bpt)­(H₂O)₂]­[(4,4′-H₂bmib)_0.5]·H₂O}_<i>n</i> (<b>6</b>), {[Cu­(bpt)_0.5(4,4′-bimbp)]·H₂O}_<i>n</i> (<b>7</b>), {[Co­(H₂bpt)­(2,7-dfo)]·H₂O}_<i>n</i> (<b>8</b>), and {[Ni₂(bpt)­(4,4′-bibp)_2.5(H₂O)]·3­(H₂O)}_<i>n</i> (<b>9</b>) (Hpptp = 2-(3-(4-(pyridin-4-yl)­phenyl)-1<i>H</i>-1,2,4-triazol-5-yl)­pyridine; 4,4′-bmib = 4,4′-bis­(2-methylimidazol-1-yl)­benzene; 4,4′-bimbp = 4,4′-bis­(imidazol-1-ylmethyl)­biphenyl; 2,7-dfo = 2,7-di­(imidazo-1-ly)-9<i>H</i>-fluoren-9-one; 4,4′-bibp = 4,4′-bis­(imidazol)­biphenyl). Their structures have been determined by single-crystal X-ray diffraction analyses, elemental analyses, IR spectra, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analyses. Complexes <b>1</b>–<b>4</b> are isomorphism and feature a similar 2-fold interpenetrating 2D helical double layer, which is further extended via the interlayer π···π interactions into a 3D supramolecular structure. Complex <b>5</b> displays a pillared-layer 3D porous network with a (6².8)₂(6².8².10²) topology. Compound <b>6</b> shows an unprecedented 3D host-framework consisting of Zn₆ clusters and exhibits a novel 3D (5,5,5,6,9)-connected topological net with the Schläfli symbol of (4¹⁰.6⁵)­(4¹⁹.6¹⁶.8)­(4⁶.6⁴)­(4⁷.6³)₂. The topology of <b>7</b> is an unprecedented binodal (4,4)-connected 3D network with the Schläfli symbol of (6².8⁴)­(4².8²)₂. Complex <b>8</b> exhibits a 3D (6⁶) structure with left- and right-handed helical chains arranged alternately. Complex <b>9</b> is a novel trinodal (4,4,5)-connected 3D framework with the Schläfli symbol of (6⁴.8²)­(6⁵.8)­(6⁸.8²). To the best of our knowledge, the 3D frameworks with (5,5,5,6,9)-connected net for <b>6</b>, binodal (4,4)-connected for <b>7</b>, and trinodal (4,4,5)-connected for <b>9</b> have never been documented to date. Moreover, the luminescent properties of <b>4</b> and <b>6</b> have been investigated