Published in "Crystal Growth & Design 18(2): 1215–1226, 2018" which should be cited to refer to this work. Threading Salen-type Cu- and Ni-Complexes into One-Dimensional Coordination Polymers: Solution versus Solid State and the Size Effect of the Alkali Metal Ion Alba Finelli,† Nelly Herault,́ † Aurelień Crochet,‡ and Katharina M. Fromm*,† † ‡ Department of Chemistry and FriMat, Department of Chemistry, University of Fribourg, Ch. du Museé 9, 1700 Fribourg, Switzerland *S Supporting Information ABSTRACT: Compartmentalization of metal ions is crucial in biology as well as in materials science. For the synthesis of single source precursors, the preorganization of different metal ions is of particular interest for the low- temperature generation of mixed metal oxides. On the basis of a potentially Ω- shaped salen-type ligand providing an N2O2 as well as an O2O2 coordination site, mixed metal coordination compounds with Cu(II) or Ni(II) and alkali metal ions have been studied for their structural and optical properties. UV− vis and 1H NMR titrations show that the obtained compounds adopt partially different structures in solution compared to the solid state. In the latter case, the coordination geometry is mainly governed by the size of the alkali metal ion as well as the transition metal ion used. − ■ INTRODUCTION ions22,45 47 and originating macrocycle-type compounds. The latter combination can lead to new properties48,49 in The precise arrangement and compartmentalization of metal 50−54 ions are important both in biology as well as in materials compounds such as coordination polymers, mono- and − 55−63 64−67 science.1 5 Siderophores such as iron chelators produced by multimetallic complexes or oxide materials. microbes are for example prototypes for metal specific uptaking Several structural studies were undertaken on bi- or ff 33−37 agents. These could be used in industrial or environmental trinuclear mono- or heterometallic Schi base complexes. cleanup processes to selectively extract metal ions.6 Artificial Interesting trinuclear structures of Zn-salen based complexes systems such as salen (N,N′-disalicylidene-ethylenediamine) were reported in Cai’s work, by tuning the counterions, the and its derivatives are commonly employed as versatile chelate solvent, or the reaction conditions.68 A structural description of ligands in coordination chemistry and obtained by a a binuclear Zn complex able to undergo transmetalation as well straightforward condensation reaction.7 Containing two Schiff as polynuclear salen compounds was presented by Kleij and co- base8 coordinating moieties, this family of ligands is able to workers.69,70 On the basis of salen-type ligands, Nabeshima et − http://doc.rero.ch bind to transition-metal ions in a tetradentate fashion forming al. have described multiple-metal containing host guest stable complexes through its N2O2 site. Furthermore, they complexes using transmetalation reactions to incorporate the 9 represent versatile ligands type thanks to their tunable design. guest ions.22,71 These ligands can adopt, depending on the ionic Numerous mono-, di-, or trinuclear complexes have been radius of the metal ions, a helical conformation in solution.72,73 synthesized with different transition elements exhibiting diverse fi ffi − They also reported the rst e cient and selective introduction properties.10 17 The resulting compounds are employed, e.g., ff 18,19,18,19 18,19 of three di erent metal ions into one ligand under as catalysts, for various organic reactions, as thermodynamic control.4 While numerous transition metal supramolecular building blocks,20,21 in nonlinear optical − − ions were widely employed along with the salen-derived ligands materials22 24 or as interesting magnetic compounds25 30 and − for multiple purposes, the series with alkali metal ions remain many other applications.31,32 Bermejo et al.33 37 have studied however not entirely investigated.21,74,75 Previous tests to use Mn-Schiff base complexes as possible catalysts for the − 38 41 alkali ions as guests in larger H2L salen-type ligands using also disproportionation of hydrogen peroxide. Furthermore, 72 other interesting features such as metal-containing gels and transmetalation were unsuccessful. While a recent publication nanofibers made through supramolecular assembly of Zn-salen by the Nabeshima group deals with the formation of alkali based complexes have been described by MacLachlan and co- metal ion complexes with macrocyclic ligands in solution, no − workers.42 44 Functional compartments can also be created by substitution of the ligand, allowing the coordination of two different metal 1 solid state data could be obtained to gain further proof and generating a second recognition site, O2O2, able to accept insight.76 further metal ions. Here, we report on the study of a salen derivative, H2L, The ligand H2L was synthesized following the literature synthesized from o-vanillin and ethylene diamine.77 This ligand procedure77 from the 2-hydroxy-3-methoxybenzaldehyde (o- is composed by moieties which potentially allow the vanillin) and ethane-1,2-diamine by a nucleophilic addition coordination of two different types of metal ions. The central forming an hemiaminal. The subsequent dehydration provides coordination site is an imine-based N2O2 entity which was used the resulting imine in quantitative yield (Scheme 1). to coordinate to copper(II) or nickel(II) under deprotonation. Synthesis of the Metallo-ligands. In the first step, Ni(II) This prearranges the ligand into a Ω-shape leading to a second and Cu(II) have been used to bind to the N2O2 cavity of L, 83−86 recognition site, O2O2, composed by two phenoxy and two yielding literature-known compounds LNi and LCu, used methoxy functions. Due to the high coordination aptitude of further as ligands for alkali metal ions (detailed data on all the the negatively charged phenolates formed upon deprotonation, individual titrations can be found in the Supporting the binding of hard metal ions (alkali, alkaline earth, etc.) is Information, Figures S2−S4). Solid state structures of the more favorable.78 Depending on the size of the metal ion to be compounds LCu and LNi obtained as single crystals confirm Ω coordinated in the O2O2 site, the choice of the counterions, and the binding of the metal ions in the N2O2 pocket of the - the solvent, different coordination modes can be expected in shaped ligand45,87,88 (Figure S1). The difference between the solution and/or in the solid state.74,79 A total of 11 new two complexes is that in LCu, a water molecule coordinates the compounds have been obtained and characterized to provide copper ion in order to yield a square pyramidal environment, more details and information compared to previous works. while the nickel ion in LNi remains with a square planar Containing two different Schiff base coordinating moieties, our coordination. We used these compounds to study the influence copper(II) or nickel(II) complexes are versatile chelate ligands of alkali metal ion binding in the remaining O2O2 cavity. 80 for the uptake of larger cations such as rubidium or cesium. Binding of Alkali Metal Ions to the O2O2 Recognition We also studied the structural differences influenced by the Site − Solution Studies. The second metal ion insertion was uptake of alkali metal ions between the nickel(II) and investigated by mixing LCu or LNi with the alkali metal salts. copper(II) complexes. Indeed, the copper ion tends to adopt Stoichiometric amounts were used in a solvent mixture of 1 a square pyramidal coordination sphere, while the nickel ion is ACN/EtOH for 3 h at RT. H NMR and UV−vis titrations preferentially coordinated in a quasi-perfect square planar have been performed for the LNi, respectively, the LCu derived fashion. We also studied the influence of the solvent and the compounds, to explore the formation of the different counterions upon coordination of the alkali metal compounds heterometallic complexes in solution. Indeed, the Cu(II) by the copper, respectively, the nickel salen complex, as well as compounds are paramagnetic and change color upon addition their possible structural isomers in solution and in the solid of the alkali metal ion, while the Ni(II) complexes do not state. Taken together, the structural studies of the herein change color and are diamagnetic. 1H NMR Study. described alkali-bimetallic complexes in the solid state and in M2 Coordination Studies. Upon addition solution represent an important step toward the comprehen- of aliquots of alkali metal ion salt to the solution of LNi, peak sion of the salen-based complex chemistry. shifts were observed particularly for the imine and methyl signals. For the alkali metal ions Na(I) and K(I), high-field RESULTS AND DISCUSSION shifts of the imine signals were observed, while for the two ■ larger ones, Rb(I) and Cs(I), low-field shifts signal a shielding The N2O2 imine-based chelating site of salen-based compounds effect, rendering the proton less sensitive to the magnetic field. such as H2L has the property to perfectly bind transition metal For the titration of LNi with Li(I) ions, no apparent plateau is ions.81,82 After deprotonation and complexation to divalent d- reached as the shifts are too small to determine any tendency. block transition metal ions such as Cu(II) and Ni(II) ions, This might be explained by the fact that the addition of lithium http://doc.rero.ch neutral compounds are obtained. Our symmetric ligand H2L ions can apparently, due to its smaller size, lead to the (Scheme 1) comprises two imines, two phenol, and two formation of many complex species in solution. methoxy groups. The coordination of the N2O2 moiety to a The binding isotherm for Na(I) shows a plateau at 0.5 equiv transition metal ion preorganizes the ligand in a Ω-shape, of metal ion, corresponding to 0.66 on the Job plot and hence confirming the presence of a 2:1 (LM1/M2 ratio) species in fi Scheme 1.