Control of Self-Penetration and Dimensionality in Luminescent Cadmium Succinate Coordination Polymers via Isomeric Dipyridylamide Ligands

Reaction in aqueous solution of cadmium nitrate, succinic acid (H₂suc), and one of four possible isomeric dipyridylamide coligands has afforded a series of two-dimensional (2-D) and three-dimensional (3-D) coordination polymers. All were structurally characterized by single-crystal X-ray diffraction. [Cd­(suc)­(4-pina)]_<i>n</i> (<b>1</b>, 4-pina = 4-pyridylisonicotinamide) displays a 3-D 6-connected self-penetrated 4⁴6¹⁰8 <b>mab</b> topology, while {[Cd­(suc)­(3-pna)]·2.5H₂O}_<i>n</i> (<b>2</b>, 3-pna = 3-pyridylnicotinamide) has a simple 3-D non-interpenetrated 4¹²6³ <b>pcu</b> network. The supramolecular isomer <b>2′</b> has exactly the same stoichiometry and overall <b>pcu</b> topology as <b>2</b> but shows a difference in succinate binding mode. Compounds <b>1</b>, <b>2</b>, and <b>2′</b> all show similar [Cd­(suc)]_<i>n</i> layers with embedded {Cd₂O₂} rhomboid dimers that serve as the 6-connected nodes. {[Cd­(suc)­(4-pna)­(H₂O)]·2H₂O}_<i>n</i> (<b>3</b>, 4-pna = 4-pyridylnicotinamide) manifests an extremely rare 2-D 4-connected 6⁶ layer self-penetrated topology based on cross-pillared [Cd­(suc)]_<i>n</i> helical chains. Slight adjustment of the donor disposition resulted in the formation of the 2-D (4,4) grid coordination polymer {[Cd­(suc)­(3-pina)­(H₂O)]·3.5H₂O}_<i>n</i> (<b>4</b>, 3-pina = 3-pyridylisonicotinamide), which has [Cd­(suc)]_<i>n</i> helical chains similar to those in <b>3</b> but avoids cross-pillaring. Luminescent and thermal properties of these four new materials are discussed

Control of Self-Penetration and Dimensionality in Luminescent Cadmium Succinate Coordination Polymers via Isomeric Dipyridylamide Ligands

Reaction in aqueous solution of cadmium nitrate, succinic acid (H₂suc), and one of four possible isomeric dipyridylamide coligands has afforded a series of two-dimensional (2-D) and three-dimensional (3-D) coordination polymers. All were structurally characterized by single-crystal X-ray diffraction. [Cd­(suc)­(4-pina)]_<i>n</i> (<b>1</b>, 4-pina = 4-pyridylisonicotinamide) displays a 3-D 6-connected self-penetrated 4⁴6¹⁰8 <b>mab</b> topology, while {[Cd­(suc)­(3-pna)]·2.5H₂O}_<i>n</i> (<b>2</b>, 3-pna = 3-pyridylnicotinamide) has a simple 3-D non-interpenetrated 4¹²6³ <b>pcu</b> network. The supramolecular isomer <b>2′</b> has exactly the same stoichiometry and overall <b>pcu</b> topology as <b>2</b> but shows a difference in succinate binding mode. Compounds <b>1</b>, <b>2</b>, and <b>2′</b> all show similar [Cd­(suc)]_<i>n</i> layers with embedded {Cd₂O₂} rhomboid dimers that serve as the 6-connected nodes. {[Cd­(suc)­(4-pna)­(H₂O)]·2H₂O}_<i>n</i> (<b>3</b>, 4-pna = 4-pyridylnicotinamide) manifests an extremely rare 2-D 4-connected 6⁶ layer self-penetrated topology based on cross-pillared [Cd­(suc)]_<i>n</i> helical chains. Slight adjustment of the donor disposition resulted in the formation of the 2-D (4,4) grid coordination polymer {[Cd­(suc)­(3-pina)­(H₂O)]·3.5H₂O}_<i>n</i> (<b>4</b>, 3-pina = 3-pyridylisonicotinamide), which has [Cd­(suc)]_<i>n</i> helical chains similar to those in <b>3</b> but avoids cross-pillaring. Luminescent and thermal properties of these four new materials are discussed

Control of Self-Penetration and Dimensionality in Luminescent Cadmium Succinate Coordination Polymers via Isomeric Dipyridylamide Ligands

Reaction in aqueous solution of cadmium nitrate, succinic acid (H₂suc), and one of four possible isomeric dipyridylamide coligands has afforded a series of two-dimensional (2-D) and three-dimensional (3-D) coordination polymers. All were structurally characterized by single-crystal X-ray diffraction. [Cd­(suc)­(4-pina)]_<i>n</i> (<b>1</b>, 4-pina = 4-pyridylisonicotinamide) displays a 3-D 6-connected self-penetrated 4⁴6¹⁰8 <b>mab</b> topology, while {[Cd­(suc)­(3-pna)]·2.5H₂O}_<i>n</i> (<b>2</b>, 3-pna = 3-pyridylnicotinamide) has a simple 3-D non-interpenetrated 4¹²6³ <b>pcu</b> network. The supramolecular isomer <b>2′</b> has exactly the same stoichiometry and overall <b>pcu</b> topology as <b>2</b> but shows a difference in succinate binding mode. Compounds <b>1</b>, <b>2</b>, and <b>2′</b> all show similar [Cd­(suc)]_<i>n</i> layers with embedded {Cd₂O₂} rhomboid dimers that serve as the 6-connected nodes. {[Cd­(suc)­(4-pna)­(H₂O)]·2H₂O}_<i>n</i> (<b>3</b>, 4-pna = 4-pyridylnicotinamide) manifests an extremely rare 2-D 4-connected 6⁶ layer self-penetrated topology based on cross-pillared [Cd­(suc)]_<i>n</i> helical chains. Slight adjustment of the donor disposition resulted in the formation of the 2-D (4,4) grid coordination polymer {[Cd­(suc)­(3-pina)­(H₂O)]·3.5H₂O}_<i>n</i> (<b>4</b>, 3-pina = 3-pyridylisonicotinamide), which has [Cd­(suc)]_<i>n</i> helical chains similar to those in <b>3</b> but avoids cross-pillaring. Luminescent and thermal properties of these four new materials are discussed

Control of Self-Penetration and Dimensionality in Luminescent Cadmium Succinate Coordination Polymers via Isomeric Dipyridylamide Ligands

Reaction in aqueous solution of cadmium nitrate, succinic acid (H₂suc), and one of four possible isomeric dipyridylamide coligands has afforded a series of two-dimensional (2-D) and three-dimensional (3-D) coordination polymers. All were structurally characterized by single-crystal X-ray diffraction. [Cd­(suc)­(4-pina)]_<i>n</i> (<b>1</b>, 4-pina = 4-pyridylisonicotinamide) displays a 3-D 6-connected self-penetrated 4⁴6¹⁰8 <b>mab</b> topology, while {[Cd­(suc)­(3-pna)]·2.5H₂O}_<i>n</i> (<b>2</b>, 3-pna = 3-pyridylnicotinamide) has a simple 3-D non-interpenetrated 4¹²6³ <b>pcu</b> network. The supramolecular isomer <b>2′</b> has exactly the same stoichiometry and overall <b>pcu</b> topology as <b>2</b> but shows a difference in succinate binding mode. Compounds <b>1</b>, <b>2</b>, and <b>2′</b> all show similar [Cd­(suc)]_<i>n</i> layers with embedded {Cd₂O₂} rhomboid dimers that serve as the 6-connected nodes. {[Cd­(suc)­(4-pna)­(H₂O)]·2H₂O}_<i>n</i> (<b>3</b>, 4-pna = 4-pyridylnicotinamide) manifests an extremely rare 2-D 4-connected 6⁶ layer self-penetrated topology based on cross-pillared [Cd­(suc)]_<i>n</i> helical chains. Slight adjustment of the donor disposition resulted in the formation of the 2-D (4,4) grid coordination polymer {[Cd­(suc)­(3-pina)­(H₂O)]·3.5H₂O}_<i>n</i> (<b>4</b>, 3-pina = 3-pyridylisonicotinamide), which has [Cd­(suc)]_<i>n</i> helical chains similar to those in <b>3</b> but avoids cross-pillaring. Luminescent and thermal properties of these four new materials are discussed

Control of Self-Penetration and Dimensionality in Luminescent Cadmium Succinate Coordination Polymers via Isomeric Dipyridylamide Ligands

Reaction in aqueous solution of cadmium nitrate, succinic acid (H₂suc), and one of four possible isomeric dipyridylamide coligands has afforded a series of two-dimensional (2-D) and three-dimensional (3-D) coordination polymers. All were structurally characterized by single-crystal X-ray diffraction. [Cd­(suc)­(4-pina)]_<i>n</i> (<b>1</b>, 4-pina = 4-pyridylisonicotinamide) displays a 3-D 6-connected self-penetrated 4⁴6¹⁰8 <b>mab</b> topology, while {[Cd­(suc)­(3-pna)]·2.5H₂O}_<i>n</i> (<b>2</b>, 3-pna = 3-pyridylnicotinamide) has a simple 3-D non-interpenetrated 4¹²6³ <b>pcu</b> network. The supramolecular isomer <b>2′</b> has exactly the same stoichiometry and overall <b>pcu</b> topology as <b>2</b> but shows a difference in succinate binding mode. Compounds <b>1</b>, <b>2</b>, and <b>2′</b> all show similar [Cd­(suc)]_<i>n</i> layers with embedded {Cd₂O₂} rhomboid dimers that serve as the 6-connected nodes. {[Cd­(suc)­(4-pna)­(H₂O)]·2H₂O}_<i>n</i> (<b>3</b>, 4-pna = 4-pyridylnicotinamide) manifests an extremely rare 2-D 4-connected 6⁶ layer self-penetrated topology based on cross-pillared [Cd­(suc)]_<i>n</i> helical chains. Slight adjustment of the donor disposition resulted in the formation of the 2-D (4,4) grid coordination polymer {[Cd­(suc)­(3-pina)­(H₂O)]·3.5H₂O}_<i>n</i> (<b>4</b>, 3-pina = 3-pyridylisonicotinamide), which has [Cd­(suc)]_<i>n</i> helical chains similar to those in <b>3</b> but avoids cross-pillaring. Luminescent and thermal properties of these four new materials are discussed

Structural Chemistry and Properties of Metal Oxalates Containing a Long-Spanning Dipyridyl Ligand: Chain, Interpenetrated Diamondoid, Threaded-Loop Layer, and Self-Penetrated Topologies

Hydrothermal reaction of metal oxalate (ox) salts and bis­(4-pyridylmethyl)­piperazine (bpmp) afforded a series of coordination polymers that were structurally characterized by single-crystal X-ray diffraction. {[Cd­(H₂O)₄(bpmp)]­(ox)}_<i>n</i> (<b>1</b>) and {[Co­(H₂O)₄(bpmp)]­(ox)}_<i>n</i> (<b>2</b>) show isostructural cationic one-dimensional (1D) coordination polymer chain motifs with unligated ox anions. A higher temperature polymorph of <b>2</b>, {[Co­(ox)­(bpmp)]·3H₂O}_<i>n</i> (<b>3</b>), possesses a system of threefold interpenetrated three-dimensional (3D) diamondoid nets. {[Mn­(H₂O)₄(bpmp)] [Mn₂(ox)₃]·5H₂O}_<i>n</i> (<b>4</b>) manifests a unique 1D + 2D → 3D polyrotaxane coordination polymer structure with 1D cationic [Mn­(H₂O)₄(bpmp)]_<i>n</i> chains threaded through apertures coursing through parallel stacks of anionic [Mn₂(ox)₃]_<i>n</i> two-dimensional (2D) hexagonal layers. {[Cu₂(ox)₂(bpmp)]·6H₂O}_<i>n</i> (<b>5</b>) possesses 2D [Cu₂(ox)₂]_<i>n</i> layers pillared by bpmp ligands into a 3D [Cu₂(ox)₂(bpmp)]_<i>n</i> coordination polymer network with an unprecedented 4,4-connected self-penetrated (5³8³)₂(5⁴8²) topology. Variable temperature magnetic susceptibility studies showed weak antiferromagnetic coupling along [Co­(ox)]_<i>n</i> chain submotifs in <b>3</b> with concomitant zero-field splitting (<i>J</i> = −4.1(7) cm^–1, <i>D</i> = 34.5(6) cm^–1), weak antiferromagnetic coupling within the [Mn₂(ox)₃]_<i>n</i> hexagonal layers in <b>4</b> (<i>J</i> ∼ −0.5 cm^–1), and strong antiferromagnetic coupling within the 2D [Cu₂(ox)₂]_<i>n</i> layers in <b>5</b> (<i>J</i> = −220(6) cm^–1)

Diverse Topologies in Chiral Divalent Metal Camphorate Coordination Polymers Containing 4,4′-Dipyridylamine

Hydrothermal synthesis has afforded six chiral divalent metal coordination polymers containing d-camphorate (d-cmph) and 4,4′-dipyridylamine (dpa) ligands, whose topologies depend largely on metal coordination geometry preference. Both cadmium derivatives {[Cd­(dpa)­(d-cmphH)₂(H₂O)]·0.875H₂O}_<i>n</i> (<b>1</b>) and {[Cd­(d-cmph)­(dpa)­(Hdpa)]­ClO₄}_<i>n</i> (<b>1a</b>) exhibit one-dimensional (1-D) chains with protonated pendant ligands; <b>1</b> possesses sinusoidal chains with a “wavelength” of over 67 Å. [Zn₂(d-cmph)₂(dpa)­(H₂O)]_<i>n</i> (<b>2</b>) exhibits a two-dimensional (2-D) 3,4-connected binodal net with (5³)₂(5⁴8²) topology. {[Ni­(d-cmph)­(dpa)]·3H₂O}_<i>n</i> (<b>3</b>) and {[M₂(d-cmph)₂(dpa)]·H₂O}_<i>n</i> (M = Co, <b>4</b>; M = Cu, <b>5</b>) manifest three-dimensional (3-D) networks. The nickel derivative has an uncommon 2-fold interpenetrated 4-connected 4²8⁴ <b>lvt</b> topology, while the isostructural cobalt and copper complexes possess 6-connected <b>pcu</b> topologies based on {M₂(OCO)₄} paddlewheel dimers. Complexes <b>1/1a</b> and <b>2</b> undergo visible light emission upon ultraviolet excitation. Variable temperature magnetic susceptibility experiments indicate weak (<i>J</i> = −3.6(2) cm^–1) and strong (<i>J</i> = –202(5) cm^–1) antiferromagnetic coupling for <b>4</b> and <b>5</b>, respectively