A Chain-of-Dimers Anion in a Novel Hybrid Halometallate (C5H14N2)3{Sb2Br9}2 Exhibiting Photoluminescence Atypical for One-Dimensional Anions Features

A Chain-of-Dimers Anion in a Novel Hybrid Halometallate (C5H14N2)3{Sb2Br9}2 Exhibiting Photoluminescence Atypical for One-Dimensional Anions Features Full article

Journal

Dalton Transactions
ISSN: 1477-9234 , E-ISSN: 1477-9226

Output data

Year: 2025, Volume: 54, Pages: 1541-1551 Pages count : 11 DOI: 10.1039/d4dt02751e

Authors

Bykov Andrei V ¹ , Shestimerova Tatiana A ¹ , Bykov Mikhail A ¹ , Gontcharenko Victoria E ^2,3 , Lyssenko Konstantin A ¹ , Metlin Mikhail T ³ , Taydakov Ilya V ^4,3 , Grigorieva Anastasia V ^1,5 , Shevelkov Andrei V ¹

Affiliations

1	Department of Chemistry, Lomonosov Moscow State University, 119991 Moscow, Russia. shev@inorg.chem.msu.ru.
2	Faculty of Chemistry, National Research University Higher School of Economics, 101000 Moscow, Russia.
3	P.N. Lebedev Physical Institute of the Russian Academy of Sciences, 119991 Moscow, Russia.
4	N.D. Zelinsky Institute of Organic Chemistry Russian Academy of Sciences, 119991 Moscow, Russia.
5	Faculty of Materials Science, Lomonosov Moscow State University, 119991 Moscow, Russia.

In pursuit of identifying less toxic hybrid compounds suitable for optoelectronic applications, we synthesized a novel homopiperazinium bromoantimonate(III), (C5H14N2)3{Sb2Br9}2. It readily crystallized from an aqueous hydrobromic acid solution and was found to be stable both in air and upon heating up to 175 °C. The crystal structure of the new bromoantimonate(III) consisted of {Sb2Br9}3− zigzag chains, which were composed of strongly trigonally distorted SbBr63− octahedral anions and C5H14N22+ dications. Weak interactions, including (N)H⋯Br hydrogen bonds and Br⋯Br van der Waals contacts, facilitated the assembly of the structural moieties into a three-dimensional (3D) supramolecular framework. The photoluminescence (PL) spectrum of (C5H14N2)3{Sb2Br9}2 displayed two broad bands in visible and near-infrared regions, which were scarcely detectable at room temperature but gained intensity upon cooling. Red emission at 645 nm, typically observed in zero-dimensional halometallates, was attributed to antimony 5s2 lone-pair-driven luminescence that corresponded to the emission from the self-trapped exciton (STE) state. The title compound also exhibited an atypical PL band at 880 nm, which has been discussed along with the optical properties and Raman spectrum of (C5H14N2)3{Sb2Br9}2.

Bykov A.V. , Shestimerova T.A. , Bykov M.A. , Gontcharenko V.E. , Lyssenko K.A. , Metlin M.T. , Taydakov I.V. , Grigorieva A.V. , Shevelkov A.V.
A Chain-of-Dimers Anion in a Novel Hybrid Halometallate (C5H14N2)3{Sb2Br9}2 Exhibiting Photoluminescence Atypical for One-Dimensional Anions Features
Dalton Transactions. 2025. V.54. P.1541-1551. DOI: 10.1039/d4dt02751e WOS Scopus OpenAlex

Web of science:	WOS:001372226800001
Scopus:	2-s2.0-85211986020
OpenAlex:	W4404763373

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