Ditopic Centrosymmetric Mercaptobenzothiazole Dilithium Salts: From the Molecular Complex to Luminescent 1D Metal-Organic Frameworks

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Abstract

The reaction of lithium amide LiN(Si(Me)3)2 and ditopic heterocyclic ligand benzo[1,2-d:4,5-d′]bis(thiazole)-2,6(3H,7H)-dithione (H2L) in dimethoxyethane (DME) affords the binuclear molecular complex Li2L(DME)4 (I). New compounds [[Li2L(ДМСО)4 • (ДМСО)2]n (II) and [Li2L(ДМСО)4 • (ТГФ)2]n (III) are prepared by the recrystallization of compound I using a DMSO–diethyl ether or DMSO/THF mixture of solvents, respectively. According to the XRD data, these compounds are one-dimensional metalorganic frameworks (MOFs) differed by the arrangement of the bis(thiazole) fragments relative to each other and the Li2O2 fragment in the polymer chain, which affects the luminescence properties. The molecular structures of compounds I–III are determined by XRD (CIF files CCDC nos. 2334192 (I), 2334193 (II), and 2334194 (III)).

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About the authors

A. F. Rogozhin

Razuvaev Institute of Organometallic Chemistry of the Russian Academy of Sciences

Author for correspondence.
Email: atonrog@iomc.ras.ru
Russian Federation, Nizhny Novgorod

V. A. Ilyichev

Razuvaev Institute of Organometallic Chemistry of the Russian Academy of Sciences

Email: atonrog@iomc.ras.ru
Russian Federation, Nizhny Novgorod

L. I. Silantyeva

Razuvaev Institute of Organometallic Chemistry of the Russian Academy of Sciences

Email: atonrog@iomc.ras.ru
Russian Federation, Nizhny Novgorod

E. A. Kozlova

Razuvaev Institute of Organometallic Chemistry of the Russian Academy of Sciences

Email: atonrog@iomc.ras.ru
Russian Federation, Nizhny Novgorod

G. K. Fukin

Razuvaev Institute of Organometallic Chemistry of the Russian Academy of Sciences

Email: atonrog@iomc.ras.ru
Russian Federation, Nizhny Novgorod

M. N. Bochkarev

Razuvaev Institute of Organometallic Chemistry of the Russian Academy of Sciences

Email: atonrog@iomc.ras.ru
Russian Federation, Nizhny Novgorod

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Supplementary files

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2. Scheme 1. Synthesis of Li2L(DME)4 (I)

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3. Fig. 1. Molecular structure of compound I

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4. Fig. 2. Monomeric link (a) and polymer chain fragment (b) in the crystal of compound II

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5. Fig. 3. Monomeric link (a) and polymer chain fragment (b) in the crystal of compound III

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6. Fig. 4. Mutual arrangement of bis-thiazolate ligands relative to the Li2O2 fragment in II (a) and III (b)

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7. Fig. 5. Mutual arrangement of control circuits in connections II (a) and III (b)

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8. Fig. 6. PL spectrum of solid samples I-III at T = 298 K, λvozb = 370 nm

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9. Fig. 7. PL spectrum of solid samples I-III at T = 77 K, λvozb = 310 nm

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