A Novel Noninterpenetrating Polycyclohexane Network:  A New Inorganic/Organic Coordination Polymer Structural Motif Generated by Self-Assembly of “T-Shaped” Moieties

• Published in: Chemistry of materials Vol. 12; no. 4; pp. 1156 - 1161
• Main Authors: Dong, Yu-Bin, Smith, Mark D, Layland, Ralph C, zur Loye, Hans-Conrad
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 17.04.2000
• Subjects: Applied sciences; Exact sciences and technology; Inorganic and organomineral polymers; Physicochemistry of polymers; Properties and characterization; Cobalt Complexes; Ketazine; Stacking sequence; Molecular structure; Polychelate; Organometallic polymer; Organic ligand; Experimental study; Lattice parameters; Pyridine derivatives; Cadmium Complexes; Inclusion compound; Crystalline structure
• ISSN: 0897-4756; 1520-5002
• DOI: 10.1021/cm9907965

The new bidentate nitrogen-donor ligand 1,4-bis(3-pyridyl)-2,3-diaza-1,3-butadiene (4) has been synthesized (monoclinic, P21/c, a = 11.074(2) Å, b = 4.737(1) Å, c = 11.475(2) Å, β = 115.861(9)°, V = 541.7(1) Å3, Z = 4) and its coordination chemistry with cadmium and cobalt nitrate hydrates investigated. Two new noninterpenetrating coordination polymers based on “T-shaped” building blocks have been obtained:  [Cd(NO3)2(C12H10N4)1.5·CH2Cl2] n (5) (monoclinic, P21/n, a = 7.891(1) Å, b = 17.172(3) Å, c = 18.576(4) Å, β = 97.72(1)°, V = 2494.5(7) Å3, Z = 4) and [Co(NO3)2(C12H10N4)1.5·CH2Cl2] n (6) (monoclinic, P21/n, a = 7.7954(8) Å, b = 17.026(3) Å, c = 18.412(3) Å, β = 97.89(1)°, V = 2420.6(6) Å3, Z = 4). Both 5 and 6 adopt a novel “polycyclohexane” structural motif, consisting of “all-equatorially” condensed cyclohexane-like M6(ligand)6 units. They are open-framework materials with unusually large cavities (ca. 28 × 15 Å), and reversibly absorb and desorb guest molecules between room temperature and 213 °C without framework decomposition.