Coordination Compounds of Alkali and Rare Earth Metals Based on Centrosymmetric Chlorine-Substituted Bis-Mercaptooxazole. Synthesis, Structure, and Luminescence

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Abstract

New coordination polymers were synthesized. A ditopic centrosymmetric organic ligand containing oxazole heterocycles, 4,8-dichlorobenzo[1,2d:4,5d´]bis(oxazole)-2,6(3H,7H)-dithione (H2L), was prepared and structurally characterized. It was shown that deprotonated H2L forms non-luminescent binuclear molecular complexes Li2L(THF)6 (I) and Na2L(DME)4 (II) with alkali metals, while complexes of H2L with lanthanides are ionic compounds [Ln(DMSO)8][L]1.5 (Ln = Nd (III), Yb (IV)) exhibiting moderate metalcentered emission in the near-infrared (IR) range, despite the absence of coordination of the ligand L to lanthanide ions. The molecular structures of H2L·2DMSO and I–III were established by X-ray diffraction (CCDC no. 2320461 (H2L·2DMSO), 2320462 (I), 2320463 (II), 2320464 (III)).

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About the authors

A. F. Rogozhin

Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences

Author for correspondence.
Email: atonrog@gmail.com
Russian Federation, Nizhny Novgorod

V. A. Il´ichev

Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences

Email: atonrog@gmail.com
Russian Federation, Nizhny Novgorod

L. I. Silant´eva

Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences

Email: atonrog@gmail.com
Russian Federation, Nizhny Novgorod

T. A. Kovylina

Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences

Email: atonrog@gmail.com
Russian Federation, Nizhny Novgorod

E. A. Kozlova

Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences

Email: atonrog@gmail.com
Russian Federation, Nizhny Novgorod

G. K. Fukin

Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences

Email: atonrog@gmail.com
Russian Federation, Nizhny Novgorod

M. N. Bochkareva

Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences

Email: atonrog@gmail.com
Russian Federation, Nizhny Novgorod

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Supplementary files

Supplementary Files
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2. Scheme 1. Synthesis of the ditopic ligand H₂L.

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3. Fig. 1. Molecular structure of H2L · 2DMSO. Ellipsoids with 30% probability are shown. Hydrogen atoms of DMSO are not shown for clarity.

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4. Fig. 2. Fragment of the crystal packing of the H₂L complex. The crystallographic projection along the b axis is shown. Hydrogen atoms are not shown for clarity.

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5. Scheme 2. Synthesis of binuclear alkali metal complexes I and II.

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6. Fig. 3. Molecular structure of complex I. Ellipsoids with 30% probability are shown. Hydrogen atoms are not shown for clarity. The symmetry operation ½ – x, ½ + y, ½ – z, used to generate equivalent atoms (A).

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7. Scheme 3. Synthesis of ionic compounds of lanthanides III and IV.

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8. Fig. 4. Molecular structure of complex II. Ellipsoids with 30% probability are shown. Hydrogen atoms are not shown for clarity. The symmetry operation ½ – x, ½ + y, ½ – z, used to generate equivalent atoms (A).

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9. Fig. 5. Cationic (a) and anionic (b) parts of complex III. Ellipsoids with 30% probability are shown. Hydrogen atoms are not shown for clarity.

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10. Fig. 6. The arrangement of bismercaptooxazole dianions in complex III. Ellipsoids with 30% probability are shown. Hydrogen atoms are not shown for clarity.

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11. Fig. 7. PL spectra of solid samples III and IV in the IR range at room temperature, λexc = 405 nm.

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