Varied Layer Topologies in Luminescent Zinc Coordination Polymers with Flexible Aromatic ortho‐Dicarboxylate and Dipyridyl Ligands. Issue 12 (10th July 2013)

• Record Type: Journal Article
• Authors: Murray, Nathan H.; Farnum, Gregory A.; LaDuca, Robert L.
• Is Part Of: Zeitschrift für anorganische und allgemeine Chemie. Volume 639:Issue 12/13(2013)
• Page Start: 2162
• Page End: 2170
• Publication Date: 2013-07-10
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry -- Periodicals; 540
• DOI: 10.1002/zaac.201300258
• Languages: English
• ISSNs: 0044-2313

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>Hydrothermal synthesis has afforded four divalent zinc flexible‐arm aromatic <italic>ortho</italic>‐dicarboxylate coordination polymers containing dipyridyl coligands. According to X‐ray crystallography, all four show layered coordination polymer structures. Nevertheless there is significant ligand influence on the nature of zinc atom aggregation and overall topology. In both {[Zn<sub>2</sub>(hmph)<sub>2</sub>(dpa)<sub>2</sub>]<bold>·</bold>2H<sub>2</sub>O}<italic><sub>n</sub></italic> (<bold>1</bold>) (hmph = homophthalate, dpa = 4, 4′‐dipyridylamine), and {[Zn<sub>2</sub>(hmph)<sub>2</sub>(dpe)<sub>2</sub>](ClO<sub>4</sub>)<sub>2</sub><bold>·</bold>H<sub>2</sub>dpe<bold>·</bold>4H<sub>2</sub>O}<italic><sub>n</sub></italic> (<bold>2</bold>) [dpe = bis(4‐pyridyl)ethane], large {Zn<sub>2</sub>(hmph)<sub>2</sub>} dimeric units are evident, along with an overall herringbone (6, 3) layer topology. The longer span of the dpe ligands results in larger incipient channels, which can accommodate protonated dpe dications and perchlorate counterions. In {[Zn<sub>2</sub>(hmph)<sub>2</sub>(3‐pna)]<bold>·</bold>H<sub>2</sub>O}<italic><sub>n</sub></italic> (<bold>3</bold>) (3‐pna = 3‐pyridylnicotinamide), {Zn<sub>2</sub>(OCO)<sub>2</sub>} <italic>anti‐syn</italic> bridged dimers and {Zn<sub>2</sub>(OCO)<sub>4</sub>} <italic>syn‐syn</italic> paddlewheel dimers coexist and are linked together by hmph and 3‐pna ligands into decorated (4, 4) grid coordination polymer layers. {[Zn(1, 2‐phda)(3‐pina)]<bold>·</bold>2H<sub>2</sub>O}<italic><sub>n</sub></italic> (<bold>4</bold>) (1, 2‐phda = 1, 2‐phenylenediacetate, 3‐pina = 3‐pyridylisonicotinamide) manifests an undulating (4, 4) grid structure with isolated zinc atoms; the "wavelength" of the layers measures over 40 Å. Luminescent properties of these materials are also reported.</p> </abstract>