Author: Almudena Gallego

Solvent-Induced Delamination of a Multifunctional Two Dimensional Coordination Polymer

A coordination polymer is fully exfoliated by solvent-assisted interaction only. The soft-delamination process results from the structure of the starting material, which shows a layered structure with weak layer-to-layer interactions and cavities with the ability to locate several solvents in an unselective way. These results represent a significant step forward towards the production of structurally designed one-molecule thick 2D materials with tailored physico-chemical properties.

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Reversible Solvent‐Exchange‐Driven Transformations in Multifunctional Coordination Polymers Based on Copper‐Containing Organosulfur Ligands

The preparation by simple direct synthesis of a series of coordination polymers based on copper with chloride or bromide and dipyrimidinedisulfide is reported. The structural characterisations of these compounds reveal a rich structural variety as a result of the number of coordination modes available to the organosulfur ligand, in combination with the bridging capabilities of the halides. Interestingly, some of the polymers displayed fully reversible solvent exchange/removal crystal-to-crystal 2D to 0D and 2D to 2D transformations. These materials show multifunctional electronic properties. Thus, some of them are semiconductors and present weak antiferromagnetic interactions, and the CuI/C…

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Electrical Conductivity and Luminescence in Coordination Polymers Based on Copper(I)-Halides and Sulfur-Pyrimidine Ligands

The solvothermal reactions between pyrimidinedisulfide (pym(2)S(2)) and CuI or CuBr(2) in CH(2)Cl(2):CH(3)CN lead to the formation of [Cu(11)I(7)(pymS)(4)](n) (pymSH = pyrimidine-2(1H)-thione) (1) and the dimer [Cu(II)(μ-Br)(Br)L](2) (L = 2-(pyrimidin-2-ylamino)-1,3-thiazole-4-carbaldehyde) (2). In the later reaction, there is an in situ S-S, S-C(sp(2)), and C(sp(2))-N multiple bond cleavage of the pyrimidinedisulfide resulting in the formation of 2-(pyrimidin-2-ylamino)-1,3-thiazole-4-carbaldehyde. Interestingly, similar reactions carried out just with a change in the solvent (H(2)O:CH(3)CN instead of CH(2)Cl(2):CH(3)CN) give rise to the formation of coordination polymers with rather diffe…

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Electrical Behaviour of Heterobimetallic [MM′(EtCS2)4] (MM′=NiPd, NiPt, PdPt) and MM′X-Chain Polymers [PtM(EtCS2)4I] (M=Ni, Pd)

Herein, we report the isolation of new heterobimetallic complexes [Ni0.6Pd1.4ACHTUNGTRENUNG(EtCS2)4] (1), [NiPtACHTUNGTRENUNG(EtCS2)4] (2) and [Pd0.4Pt1.6ACHTUNGTRENUNG(EtCS2)4] (3), which were constructed by using transmetallation procedures. Subsequent oxidation with iodine furnished the MM'X monodimensional chains [Ni0.6Pt1.4ACHTUNGTRENUNG(EtCS2)4I] (4) and [Ni0.1Pd0.3Pt1.6ACHTUNGTRENUNG(EtCS2)4I] (5). The physical properties of these systems were investigated and the chain structures 4 and 5 were found to be reminiscent of the parent [Pt2ACHTUNGTRENUNG(EtCS2)4I] species. However, they were more sensitively dependent on the localised nature of the charge on the Ni ion, which caused spont…

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MMX Chains and Molecular Species Containing Rh 2 n+ ( n = 4, 5, and 6) Units: Electrical Conductivity in Crystal Phase of MMX Polymers

The control of the experimental conditions in the reaction of Rh 2 (O 2 CCH 3 ) 4 with halides allows the isolation of the novel dirhodium complexes K x [Rh 2 X(O 2 CCH 3 ) 4 ] x ·4xH 2 O (X = Br, 1·4H 2 O and I, 2·4H 2 O) [Rh 2 (O 2 CCH 3 ) 4 Cl] x H 2 O (3·H 2 O), [Rh 2 (O 2 CCH 3 )Cl] x ·4xH 2 O (3·4H 2 O), and {Rh 2 (O 2 CCH 3 ) 4 I 2 ]· 4H 2 0 (4·4H 2 O) containing Rh 2 n+ (n = 4, 5 and 6) units. The X-ray structure determination of compounds 1-4 reveals the presence of dirhodium units in different oxidation states. The polyanionic complexes 1·4H 2 O and 2·4H 2 O containing Rh 2 4+ units give zig-zag chains. In contrast, the partially oxidized complexes 3·H 2 O and 3·4H 2 O containing …

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Structure and Properties of One-Dimensional Heterobimetallic Polymers Containing Dicyanoaurate and Dirhodium(II) Fragments

The synthesis and characterization of compound [Rh(2)(O(2)CEt)(4)(H(2)O)(2)] (1) and one-dimensional heterobimetallic polymers K(n){Rh(2)(O(2)CEt)(4)[Au(CN)(2)]}(n) (2) and K(n){Rh(2)(O(2)CMe)(4)[Au(CN)(2)]}(n)·4nH(2)O (3), constructed from dirhodiumtetracarboxylato units, [Rh(2)(O(2)CR)(4)](+), and dicyanoaurate, [Au(CN)(2)](-), fragments are described. In both compounds 2 and 3 the resulting polymeric chains are nonlinear and have in common similar structural parameters, although the solid state supramolecular arrangement is very different. These structural differences explain the fact that complex 2 displays aurophilic interactions while this type of interactions are absent in complex 3.…

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Solvent-Induced Delamination of a Multifunctional Two Dimensional Coordination Polymer (Adv. Mater. 15/2013)

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CCDC 883365: Experimental Crystal Structure Determination

Related Article: Almudena Gallego, Cristina Hermosa, Oscar Castillo, Isadora Berlanga, Carlos J. Gómez-García, Eva Mateo-Martí, José I. Martínez, Fernando Flores, Cristina Gómez-Navarro, Julio Gómez-Herrero, Salome Delgado, Félix Zamora|2013|Adv.Mater.|25|2141|doi:10.1002/adma.201204676

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CCDC 883368: Experimental Crystal Structure Determination

Related Article: Almudena Gallego, Cristina Hermosa, Oscar Castillo, Isadora Berlanga, Carlos J. Gómez-García, Eva Mateo-Martí, José I. Martínez, Fernando Flores, Cristina Gómez-Navarro, Julio Gómez-Herrero, Salome Delgado, Félix Zamora|2013|Adv.Mater.|25|2141|doi:10.1002/adma.201204676

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