Coordination Polymers: From struCtures to aPPliCations CHIMIA 2013, 67, Nr. 6 403 doi:10.2533/chimia.2013.403 Chimia 67 (2013) 403–410 © Schweizerische Chemische Gesellschaft Coordination Polymers and Metal–Organic Frameworks Derived from 4,4'-Dicarboxy- 2,2'-bipyridine and 4,4',6,6'-Tetracarboxy- 2,2'-bipyridine Ligands: A Personal Perspective Paul E. Kruger* Abstract: Presented herein is a personal overview of some of the contributions we have made over recent years to coordination polymer chemistry employing 2,2'-bipyridine-polycarboxylic acid ligands in conjunction with first row transition, main group or lanthanide metal ions. Primarily the discussion is centred upon the two ligands with which we have enjoyed the most success: 4,4'-dicarboxy-2,2'-bipyridine (4,4'-H dcbp) and 4,4',6,6'-tetracarboxy- 2 2,2'-bipyridine (4,4',6,6'-H tcbp). Initial discussion is focused upon the synthetic aspects of ligand formation and 4 their structural characterisation and then moves on to the synthesis of metal complexes incorporating these ligands and the coordination polymers they form. Where possible the discussion is presented from a synthetic and structural perspective with highlight given to the pertinent properties of the coordination polymers formed e.g. thermal behaviour, magnetic, luminescent or small molecule sorption properties. We end the review with some conclusions and highlight some current work with a view to future research. Keywords: 2,2'-Bipyridine · Coordination polymer · Ligand synthesis · Metal–organic framework · Sorption properties 1. Introduction electro-catalytic, to anti-proliferative and interesting magnetic (e.g. single molecule biological activity.[4] Indeed, the 2,2'-bi- magnets) and catalytic properties, then There continues to be significant inter- pyridine-poly-carboxylate based ligands the realization of coordination complexes est surrounding the synthesis and charac- have been used extensively to anchor metal with myriad properties should be possible. terization of coordination polymers be- complexes to surfaces and have found util- Simply connecting bipyridine coordinated cause of the potential applications within ity in dye-sensitised solar cell applications metal ions together through the peripheral which they may find use.[1] Porous coordi- such as within the Grätzel cell.[5] Moreover, carboxylate groups should give rise to the nation polymers, or metal–organic frame- considerable current interest surrounds formation of extended frameworks (Fig. works (MOFs), in particular attract much their use in metallo-supramolecular chem- 2). Further, hydrogen bonding between attention due to the presence of nanometre- istry incorporating the formation of both ligands through the carboxylic acid func- sized voids that may engender commercial discrete species (e.g. helicates, catenates, tionality would realise hybrid networks applications upon them such as molecular etc.)[6] and infinite coordination polymers, combining the strength of coordination separations, gas storage or sequestration, with porous analogues of the latter attract- bonding with the flexibility of hydrogen catalysis and as the active components in ing great attention as they may possess bonding. sensors.[2] potential commercial applications derived Despite these potential outcomes and The polypyridine family of ligands from their gas storage and sequestration, attracts considerable attention as signifi- catalytic, magnetic, host-guest, or sensor cant chelating ligands due to their abil- capabilities etc.[7] ity to form stable complexes with metal Our attraction to the polypyridine- ions from across the periodic table.[3] The poly-carboxylate ligands was driven by continued interest is driven by the many the fact that, in principle, each functional properties possessed by these complexes group may coordinate to every metal with- ranging from photochemical and analyti- in the periodic table in a variety of ways, cal-based materials, through catalytic and either singly or in unison, to generate in- numerable complexes. The scope of poten- tial coordinating capability of this family *Correspondence: Prof. Dr. P. E. Kruger of ligands is best exemplified by appreci- MacDiarmid Institute for Advanced Materials and ating the connectivity of the 4,4',6,6'-tcbp Nanotechnology Department of Chemistry ligand (Fig. 1). Indeed, if we couple this University of Canterbury, connectivity with the ability of the car- Private Bag 4800, Christchurch 8140 boxylate ligand coordinated to either sin- Fig. 1. The structure of 4,4',6,6'-tcbp showing New Zealand gle metal ions or to form multi-metallic Tel.: +64 3 364 2438 their potential connectivity through carboxylate E-mail: [email protected] cluster species, many of which possess and 2,2'-bipyridine coordination sites. 404 CHIMIA 2013, 67, Nr. 6 Coordination Polymers: From struCtures to aPPliCations the fascinating vista this strategy would provide, there had been only two reports in the literature where the 4,4'-H dcbp li- 2 gand was employed in the deliberate for- mation of a coordination polymer[8] before our study began although others soon fol- lowed,[9] and the 4,4',6,6'-H tcbp ligand 4 was unknown. With the inspiration to fill this void and to investigate the many prop- erties that such compounds would possess we set about the synthesis of coordination polymers featuring these ligands and pro- vide here an overview of some of our suc- cesses in this journey of discovery. 2. A New Synthetic Route to New and Known Polypyridine-poly- carboxylate Ligands To systematically study the formation and properties of numerous coordination polymers, effective, reliable and, where Fig. 2. The structures of metal complexes of 4,4'-dcbp and 4,4',6,6'-tcbp showing their potential possible, sustainable synthesis of the poly connectivity through carboxylate coordination sites to form extended coordination frameworks. -pyridine ligands are required. Prior to our modification to the synthesis of car- boxylate-containing polypyridine ligands the use of metal-based oxidants, such as K Cr O and KMnO , in corrosive media, 2 2 7 4 to generate the carboxylic acid from an appropriate alkyl polypyridines precursor was employed.[10] Whilst this approach has typically wide application, it is encum- bered by serious potential health risks and associated waste disposal issues. Indeed, a one gram scale synthesis of 4,4'-H dcbp 2 involves the slow addition of ca. 8.0 g of Fig. 3. A single (4,4) 2D hydrogen-bonded sheet in 4,4'-H dcbp with a single helix highlighted 2 K Cr O to 4,4'-dimethyl-2,2'-bipyridine in purple (left) and the 3-fold 2D→2D parallel interpenetrated hydrogen-bonded networks of 2 2 7 4,4',6,6'-H tcbp (right). The networks are shown in blue, red and green. Adapted from refs. [13] and generates litres of acidic aqueous 4 waste solution for disposal after work-up. and [14]. Reproduced by permission of the Royal Society of Chemistry. We therefore developed a simple method employing dilute aqueous nitric acid solu- metrical substituted alkyl-polypyridine 2.1 Structural Characterisation of tions (4%) following a solvothermal proto- molecules including bi-, ter- and quater- 4,4'-H dcbp and 4,4',6,6'-H tcbp 2 4 col using a Teflon-lined digestion bomb to pyridine examples. Indeed, when using Ligands give crystalline products in a single step in more forcing conditions oxidation may be When working with poly-carboxy- better yields than those achieved through accompanied by decarboxylation. For ex- polypyridine molecules it is immediately traditional methods.[11] Simple product re- ample, oxidation of 4,4',6,6'-tetramethyl- apparent that they have extremely limited covery through filtration yields a recycla- 2,2'-bipyridine in 2:1 H O/HNO solution solubility in common laboratory solvents, 2 3 ble filtrate (Scheme 1). at 160 °C is accompanied by regioselective so much so that prior to our work the This method is superior to traditional mono-decarboxylation at the 6'-carboxylic solid-state structures of both 4,4'-H dcbp 2 metal-based oxidation routes from an en- acid position to yield crystalline 4,4',6-tri- and 4,4',6,6'-H tcbp were unknown. This 4 vironmental point-of-view, as it does not carboxy-2,2'-bipyridinium nitrate hydrate insolubility then places some restriction require any subsequent work-up which in ca. 50% yield (see section 4.1).[12] This upon the synthetic methods used in the negates hazardous waste disposal issues, method is, therefore, a viable route to the formation of coordination complexes and and also allows access to novel molecules synthesis of this unsymmetrical product, polymers, as it does upon the recrystalli- that are inaccessible via these routes. It is which would be difficult to obtain through sation of the ligands. We set about to as- applicable across symmetrical and unsym- more conventional synthetic means. certain their solid-state structures through single X-ray diffraction and found that solvothermal recrystallisation was effec- Scheme 1. tive i.e. simply heating either 4,4'-H dcbp 2 Polypyridine sub- or 4,4',6,6'-H tcbp in water at 150 °C in a 4 strates used to gener- sealed Teflon-lined digestion bomb in the ate the corresponding polypyridine-poly- presence of a drop of nitric acid yielded carboxylic acids via single crystals following slow cooling aqueous nitric acid (Fig. 3).[13,14] The structure of 4,4'-H dcbp consists of oxidation under sol- 2 vothermal conditions. two-dimensional (2D) hydrogen-bonded Coordination Polymers: From struCtures to aPPliCations CHIMIA 2013, 67, Nr. 6 405 sheets of (4,4) topology.[13] Each molecule acts as a four-connector with carboxylic acid groups forming hydrogen bonds to pyridyl nitrogen atoms. Equivalent isoni- cotinic acid sub-units, i.e. crystallographi- cally equivalent halves of the 4,4'-H dcbp 2 molecules, reside on the same side of a sheet and participate in hydrogen bonding and face-to-face π∙∙∙π interactions with like isonicotinic acid sub-units.