Ionothermal Synthesis of Selenido Metalates in Tunable Aryl Alkyl Ionic Liquids (TAAILs)

We report on the first reactions of selenido germanates in tunable aryl alkyl ionic liquids (TAAILs), namely, the treatment of [K<sub>4</sub>(H<sub>2</sub>O)<sub>3</sub>][Ge<sub>4</sub>Se<sub>10</sub>] with SnCl<sub>4</sub>·5H<sub>2</sub>O in (Ph<sub>4-Br</sub>C<sub>6</sub>Im)[NTf<sub>2</sub>], (Ph<sub>4-Br</sub>C<sub>8</sub>Im)[NTf<sub>2</sub>], (Ph<sub>4-Br</sub>C<sub>12</sub>Im)[NTf<sub>2</sub>], (Ph<sub>2-Me</sub>C<sub>8</sub>Im)[NTf<sub>2</sub>], and (Ph<sub>4-OMe</sub>C<sub>8</sub>Im)(NTf<sub>2</sub>), in the presence of 2,6-dimethylmorpholine (DMMP) as a basic auxiliary agent (Ph<sub>Y-X</sub> denotes a Ph group in the 1-position of the imidazolium cation (Im); the numeral Y specifies the <i>ortho</i> (2) or <i>para</i> (4) position of a substituent X at the Ph ring; and C<i><sub>n</sub></i> denotes a linear alkyl substituent with <i>n</i> C atoms in the 3-position of the Im ring; NTf<sub>2</sub> = bis(trifluoromethan)sulfonimide). The use of different TAAILs allowed the observation of different products: (Cat)<sub>24</sub>[Ge<sub>24</sub>Sn<sub>36</sub>Se<sub>132</sub>] (<b>1</b>), (Ph<sub>2-Me</sub>C<sub>8</sub>Im)<sub>2</sub>(DMMPH)<sub>2</sub>[Ge<sub>1.4</sub>Sn<sub>4.6</sub>Se<sub>14</sub>] (<b>2</b>), (Cat)<sub>6</sub>[GeSn<sub>8</sub>Se<sub>21</sub>] (<b>3</b>), (Cat)<sub>2</sub>[Sn<sub>3</sub>Se<sub>7</sub>] (<b>4</b>), and (DMMPH)<sub>4</sub>[Ge<sub>4</sub>Se<sub>10</sub>] (<b>5</b>). The compounds comprise cations from the corresponding TAAIL or (DMMPH)<sup>+</sup>, which is the monoprotonated derivative of DMMP that forms <i>in situ</i> (note that in some cases, extreme disorder of the cations did not allow their localization on the difference <i>Fourier</i> map; these are referred to as 'Cat' in their formula). We discuss the anionic substructures in comparison to those of known compounds based on Ge, Sn, and Se atoms and report the effect of the different architectures on optical absorption properties.

Authors

Institutions

Publication Details

Journal
Inorganic Chemistry
Published
2025-12-01
DOI
https://doi.org/10.1021/acs.inorgchem.5c05009
Primary Topic
Organoselenium and organotellurium chemistry
Type
article
Field-Weighted Citation Impact
0.00
Controls
|||
ALL TIME
JAN
FEB
MAR
APR
MAY
JUN
JUL
AUG
SEP
OCT
article

Ionothermal Synthesis of Selenido Metalates in Tunable Aryl Alkyl Ionic Liquids (TAAILs)

Lukas Guggolz, Gina Stuhrmann, Swantje Lerch, Isabell Nußbruch et al.
Inorganic Chemistry
Organoselenium and organotellurium chemistry
article

Ionothermal Synthesis of Selenido Metalates in Tunable Aryl Alkyl Ionic Liquids (TAAILs)

Lukas Guggolz, Gina Stuhrmann, Swantje Lerch, Isabell Nußbruch, Thomas Straßner, Stefanie Dehnen, Zhou Wu
article en

Abstract

We report on the first reactions of selenido germanates in tunable aryl alkyl ionic liquids (TAAILs), namely, the treatment of [K<sub>4</sub>(H<sub>2</sub>O)<sub>3</sub>][Ge<sub>4</sub>Se<sub>10</sub>] with SnCl<sub>4</sub>·5H<sub>2</sub>O in (Ph<sub>4-Br</sub>C<sub>6</sub>Im)[NTf<sub>2</sub>], (Ph<sub>4-Br</sub>C<sub>8</sub>Im)[NTf<sub>2</sub>], (Ph<sub>4-Br</sub>C<sub>12</sub>Im)[NTf<sub>2</sub>], (Ph<sub>2-Me</sub>C<sub>8</sub>Im)[NTf<sub>2</sub>], and (Ph<sub>4-OMe</sub>C<sub>8</sub>Im)(NTf<sub>2</sub>), in the presence of 2,6-dimethylmorpholine (DMMP) as a basic auxiliary agent (Ph<sub>Y-X</sub> denotes a Ph group in the 1-position of the imidazolium cation (Im); the numeral Y specifies the <i>ortho</i> (2) or <i>para</i> (4) position of a substituent X at the Ph ring; and C<i><sub>n</sub></i> denotes a linear alkyl substituent with <i>n</i> C atoms in the 3-position of the Im ring; NTf<sub>2</sub> = bis(trifluoromethan)sulfonimide). The use of different TAAILs allowed the observation of different products: (Cat)<sub>24</sub>[Ge<sub>24</sub>Sn<sub>36</sub>Se<sub>132</sub>] (<b>1</b>), (Ph<sub>2-Me</sub>C<sub>8</sub>Im)<sub>2</sub>(DMMPH)<sub>2</sub>[Ge<sub>1.4</sub>Sn<sub>4.6</sub>Se<sub>14</sub>] (<b>2</b>), (Cat)<sub>6</sub>[GeSn<sub>8</sub>Se<sub>21</sub>] (<b>3</b>), (Cat)<sub>2</sub>[Sn<sub>3</sub>Se<sub>7</sub>] (<b>4</b>), and (DMMPH)<sub>4</sub>[Ge<sub>4</sub>Se<sub>10</sub>] (<b>5</b>). The compounds comprise cations from the corresponding TAAIL or (DMMPH)<sup>+</sup>, which is the monoprotonated derivative of DMMP that forms <i>in situ</i> (note that in some cases, extreme disorder of the cations did not allow their localization on the difference <i>Fourier</i> map; these are referred to as 'Cat' in their formula). We discuss the anionic substructures in comparison to those of known compounds based on Ge, Sn, and Se atoms and report the effect of the different architectures on optical absorption properties.

Inorganic ChemistryVol. 64(49)
Karlsruhe Institute of Technology (DE), Philipps University of Marburg (DE), Technische Universität Dresden (DE)
Openalex Percentile: Top 62%
Organoselenium and organotellurium chemistry
DOIOpen Access PDFOpenAlex
AI Navigator

Ask Laika to Summarize, Analyze, and Connect papers live on the map.

Summarize Papers & Methodologies

Extract key findings, datasets, and comparative methods across publications.

Benchmark Rankings & Visual Analytics

Rank top research institutions, authors, funders, topics, and journals by Field-Weighted Citation Impact (FWCI) and paper volume with instant charts.

Connect Distant Disciplines

Bridge topological clusters on the map to find hidden collaborative intersections.