PAPER www.rsc.org/dalton | Dalton Transactions Alcoholysis/hydrolysis of 1,1¢-carbonyldiimidazole as a means of preparing unprecedented, imidazole-containing one-dimensional coordination polymers of copper(II)† Theocharis C. Stamatatos, a,b Spyros P. Perlepes, a Catherine P. Raptopoulou, c Aris Terzis, c Costas S. Patrickios, b Anastasios J. Tasiopoulos b and Athanassios K. Boudalis* c Received 14th January 2009, Accepted 18th February 2009 First published as an Advance Article on the web 16th March 2009 DOI: 10.1039/b900716d The use of 1,1¢-carbonyldiimidazole, (im) 2 CO, for the synthesis of imidazolate (im - ) and/or imidazole (Him)-containing copper(II) coordination polymers is described. The [Cu 2 (O 2 CMe) 4 (H 2 O) 2 ]/(im) 2 CO reaction system in EtOH yields the new polymeric species [Cu(O 2 CMe)(im)(Him)(EtOH)] n (1) and the known compound [Cu(im) 2 ] n (2), depending on the reaction conditions. A mechanism for the alcoholysis/hydrolysis of (im) 2 CO is proposed. Complex 1 comprises neutral, zigzag chains with the h 1 :h 1 :m im - ligand bridging two neighbouring Cu II atoms. Each square pyramidal metal centre is coordinated to two imidazolate nitrogen atoms, the pyridine-type nitrogen atom of the terminal imidazole ligand, one acetate oxygen atom and the ethanol oxygen atom. The dc magnetic susceptibility data for 1 have been analysed according to the Bonner-Fisher model for an equally spaced S = 1/2 chain, revealing moderate antiferromagnetic Cu II ◊◊◊ Cu II exchange interactions (J = -33.5 cm -1 using the H = -2J ∑ ˆ S i ˆ S i+1 spin Hamiltonian). The reaction system Cu(NO 3 ) 2 ·3H 2 O/(im) 2 CO in EtOH leading to the preparation of known trans-[Cu(NO 3 ) 2 (Him) 4 ](3) is also described. With terephthalate(-2) (tp 2- ), instead of MeCO 2 - , in MeOH/H 2 O the product is the new, 1D linear coordination polymer [Cu(tp)(Him) 2 (H 2 O)] n ·2nH 2 O(4·2nH 2 O). Adjacent square pyramidal Cu II atoms are singly bridged by the bis-monodentate tp 2- ligand, while two monodentate Him groups and one H 2 O molecule complete five-coordination at each metal centre. The chains of 1 and 4·2nH 2 O form interesting, hydrogen-bonded 3D networks. The combined work demonstrates the usefulness of (im) 2 CO in the preparation of interesting Cu II coordination polymers which can not be obtained by the use of Him. Introduction The utilisation of organic polymers, mainly composed of the elements C, H, O, N and—to a lesser extent—some neighbouring main group elements such as B, Si, P and S, in the 1960s transformed the way in which we live. In the field of polymers, the metallic elements, which comprise more than half of the elements in the Periodic Table, had comparatively less to contribute until the early 1990s. 1 However, this situation has changed in the last 15 years; the reason is that metal ions have attractive features for new generations of metalloorganic polymers, which are also known 2 as coordination polymers, 3a metal-organic coordination networks, metal-organic frameworks 3b or organic-inorganic hy- brid coordination polymers. To date, scientists have realised var- ious applications of coordination polymers in catalysis, electrical conductivity, luminescence, magnetism, non-linear optics, molec- ular electronics, sensing, drug delivery and zeolitic behaviour. 2,4,5 a Department of Chemistry, University of Patras, 265 04, Patras, Greece b Department of Chemistry, University of Cyprus, 264 43, Nicosia, Cyprus c Institute of Materials Science, NCSR “Demokritos”, 153 10, Aghia Paraskevi Attikis, Greece. E-mail: tbou@ims.demokritos.gr; Tel: +30 210 6503346 † CCDC reference numbers 715757 for 1 and 715758 for 4. For crystallo- graphic data in CIF or other electronic format see DOI: 10.1039/b900716d The ultimate goal is the transformation of few coordination poly- mers to functional molecular materials. Coordination polymers are also significant from a structural chemistry perspective with new, intriguing molecular topologies being discovered, as well as providing numerous examples of interesting phenomena such as the interpenetration of networks. 6 However, the factors influencing the synthesis of coordination polymers are still not completely understood and inorganic chemists are always looking for new methods that can lead to predictable products. The two main trends in the field are the ‘synthesis by design’ and the ‘non-programmed assembly’. The former involves the use of rigid, often complicated organic ligands that will ‘force’ or ‘drive’ the precipitation of the desired product. The latter approach involves the use of more flexible ligands and lacks control over the final product, but it has proven to be successful in the synthesis of polymeric compounds with interesting structures and properties. 2,4 The p-excessive and strong s-donor ligand imidazole (Him) has played a formative role in the development of coordination chemistry. 7 The imidazolate anion (im - , Scheme 1), obtained by deprotonation of Him, is capable of acting as a biden- tate bridging ligand. The 1,3-arrangement of the N atoms imposes geometrical constraints such that only one imidazo- late bridge is possible between two metal centres. Accordingly, 3354 | Dalton Trans., 2009, 3354–3362 This journal is © The Royal Society of Chemistry 2009