… rsc.org/dalt on Novel coordination polymers and structural systematics … and Christopher L. Cahill* a, b a Department of Chemistry … and hence the formation ofdandf-block organic/inorganic …FULL PAPER Dalton www.rsc.org/dalt on Novel coordination polymers and structural systematics in the hydrothermalM,M trans -3(-3-pyridyl)acrylic acid system† NoelS. Gunning a and Christopher L. Cahill* a, b aDepartment of Chemistry, George Washington University, Washington DC, USA. E-mail: cahill@gwu.edu; Fax: 202-994-5873; Tel: 202-9946959 b

There has been a steady proliferation of the synthesis of metal organic framework materials (MOFs) and coordination polymers as they spark the interests of chemists, physicists and material scientists for their novel topologies, potential applications as molecular sieves and as candidates for gas sorption, ion exchange, size-specific separation and heteroge- neouscatalysis. 1-13 As zeolitic analogues, MOFsdemonstrate similar properties; however, the ability to incorporate tailored organic and inorganic moieties within their topologies offers the possibility for more varied chemical and physical applications. Moreover, by using specific metal and ligand building blocks it is possible to predictably tune structures of varying dimensionalities in away that is absent in zeolite chemistry. Typically MOFs consist of metal centres that are tethered by multi-functional organic linkers, which give rise to a variety of building units and overall topologies. To date, a majority of these have been homometallic compounds, 14-22 but the potential to developheterometallic species makes for an attractive subject of investigation. Our approach is to utilize the hard-soft acid base classification scheme, reported by Pearson et al .,23 to govern the affinity of organic linkers for their inorganic counterparts and hence the formation ofdandf-block organic/inorganic hybrid materials. Furthermore, the electronic properties asso- ciatedwithf-block elements make them candidates for sensitized luminescence via the antenna effect. 24-28 The rational design of extended polymers has been the benchmark of this family of materials wherein their synthesis is subject to the choice of ligand, metal and reaction conditions, and to this end, the d-block/3-HPYA (3-HPYA=C 8 H 7 NO 2 )system has been previously examined 15,20-22 and demonstrates considerable structural variability. We have extended this examination to includef-block elements and the effect each metal has on the building unit and the overall architecture. In addition, we explore the fluorescence of these materials in accordance with these systematics. Reported herein are the syntheses, structures, thermal and luminescence properties of aheterometal

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