Department of Chemistry and Biochemistry

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    Conversion of lanthanide glutarate chlorides with interstitial THF into lanthanide glutarates with unprecedented topologies
    (Elsevier, 2018-02-24) Zehnder, Ralph; Jenkins, James; Zeller, Matthias; Dempsey, Christian; Kozimor, Stosh A.; Jackson, Gregory; Gilbert, Katherine; Smith, Matthew
    Using slow diffusion methods at room temperature (RT), we obtained four isomorphous lanthanide glutarate chlorides, accommodating interstitial THF and water molecules, [Ln2(Glut)2Cl2(H2O)8]•2H2O•THF (1 - 4), with Ln = La (1), Ce (2), Pr (3), Nd (4). They assemble as 3-dimensional (3D) lanthanide (Ln) coordination polymers with LnO10 coordination polyhedra. Their topology was elucidated to be a 4-coordinated sql net. 1 – 4 slowly dissolve in water liberating the entrapped THF molecules and reassemble as regular Ln-glutarate hydrates when the solution is deprived of THF and water by slow evaporation. The new products crystallize as [Ln2(Glut)3(H2O)3]•5H2O (5 - 7), with Ln = La (5), Ce (6), Pr (7), and [Nd2(Glut)3(H2O)2]•3.5H2O (8). 5 – 7 are isomorphous and crystallize as 3D-networks with two crystallographically independent LnO10 and LnO9 coordination spheres that assemble into Ln2O18 and Ln2O16 polyhedra via edge sharing. Their topology has not previously been observed and was found to be a 3,4,4,5,6-coordinated 3,4,4,5,6T61 net. The known compound 8 crystallizes also as a 3D-network and is isomorphous to other previously described lanthanide glutarate hydrates. 8 has a 3,4,5-coordinated 3,4,5T202 net topology, which has not been determined before.
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    Strain alleviation in an isomorphous series of lanthanide 2-nitroterephthalates [Ln2(TPNO2)3(H2O)2]·2H2O (Ln = Pr – Lu, except Pm)
    (Elsevier, 2017-10-01) Zehnder, Ralph; Fontaine, Nick; Mouawad, Bawdi, A.; Leonard, Jacob K.; Zeller, Matthias; Fronczek, Frank R.; de Lill, Daniel T.; Ballard, April; Bonnette, Daniel; Head, Aaron; Ghimire, Krishna; Welch, Jordan N.; Barber, Elee R.; Murray, Jared M.; Dempsey, Christian; Jenkins, James; Jackson, Gregory; Tokunboh, Mary; Bach, Stevie R.; Harris, Jaimie A. Treadway
    An extended series of trivalent lanthanide 2-nitroterephthalates, [Ln2(TPNO2)3(H2O)2]•2H2O, (Ln = Pr through Lu, except Pm) were synthesized hydrothermally from Ln2O3 and 2-nitroterephthalic acid (H2TPNO2) at 170˚C in Teflon lined Parr steel autoclaves, and were characterized via single crystal X-ray diffraction, powder X-ray diffraction, FT-IR spectroscopy, elemental analyses, and thermogravimetric analyses. All [Ln2(TPNO2)3(H2O)2]•2H2O coordination polymers are isomorphous, crystallizing in the monoclinic crystal system with space group C2/c. The metal centers in all networks possess the coordination number 8, while forming a three-dimensional extended lattice. Two metal centers form Ln2O14 entities, comprising crystallographically identical LnO8 polyhedra, connected via edge-sharing, utilizing two carboxylate O-atoms. These Ln2O14 units are separated along the a and b-axes by individual 2-nitroterephthalate linkers, while being closely connected along the c axis via two carboxylate groups on each side. Compared to small inorganic anions, the rather flexible 2-nitroterephthalate seems to allow for the unobstructed decrease in size of the LnO8 polyhedra as Ln3+ ionic radii decrease towards the heavier Ln elements. Hence, the structural parameters of the crystal lattice adjust gradually without noticeable strain buildup along the series resulting in isomorphous arrangements for all networks. The thermogravimetric and FT-IR measurements seem to confirm the structural features.