Effect of Aromatic System Expansion on Crystal Structures of 1,2,5-Thia- and 1,2,5-Selenadiazoles and Their Quaternary Salts: Synthesis, Structure, and Spectroscopic Properties

Alfuth, Jan; Zadykowicz, Beata; Sikorski, Artur; Połoński, Tadeusz; Eichstaedt, Katarzyna; Olszewska, Teresa

doi:10.3390/ma13214908

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Effect of Aromatic System Expansion on Crystal Structures of 1,2,5-Thia- and 1,2,5-Selenadiazoles and Their Quaternary Salts: Synthesis, Structure, and Spectroscopic Properties

by

Jan Alfuth

¹

,

Beata Zadykowicz

²

,

Artur Sikorski

³

,

Tadeusz Połoński

¹

,

Katarzyna Eichstaedt

¹ and

Teresa Olszewska

^1,*

¹

Department of Organic Chemistry, Gdańsk University of Technology, 80-233 Gdańsk, Poland

²

Luminescence Research Group, Faculty of Chemistry, University of Gdańsk, 80-308 Gdańsk, Poland

³

Laboratory of Crystallochemistry, Faculty of Chemistry, University of Gdańsk, 80-308 Gdańsk, Poland

^*

Author to whom correspondence should be addressed.

Materials 2020, 13(21), 4908; https://doi.org/10.3390/ma13214908

Submission received: 30 September 2020 / Revised: 23 October 2020 / Accepted: 28 October 2020 / Published: 31 October 2020

(This article belongs to the Special Issue Current Problems of the Organic Chemistry of Sulfur and Selenium)

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Abstract

Rational manipulation of secondary bonding interactions is a crucial factor in the construction of new chalcogenadiazole-based materials. This article reports detailed experimental studies on phenanthro[9,10-c][1,2,5]chalcogenadiazolium and 2,1,3-benzochalcogenadiazolium salts and their precursors. The compounds were synthesized, characterized employing NMR and UV-Vis spectroscopy. TD-DFT calculations were also performed. The influence of the size of the aromatic system on the molecular motifs formed by the compounds in the solid state has been studied by means of single-crystal X-ray diffraction. In case of the salts, the nature of an anion was also taken into consideration. The results show that cyclic [E···N]₂ supramolecular synthon connects neighboring molecules of phenanthro[9,10-c][1,2,5]chalcogenadiazoles, with a relatively large aromatic system, in dimers regardless of the chalcogen atom in the molecule. Both N-methyl-2,1,3-benzothiadiazolium and N-methylphenanthro[9,10-c][1,2,5]chalcogenadiazolium cations have a strong affinity for triflate and iodide anions, therefore the formation of S···N or Se···N secondary bonding interactions is observed only in two out of the eight quaternary salts. Less coordinating anions must be used to enable the building blocks studied to form cyclic [E···N]₂ synthons. Moreover, for two of the triflate salts, which are isostructural, a new supramolecular motif has been observed.

Keywords: chalcogenadiazoles; chalcogen bonds; crystal engineering; spectral properties

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MDPI and ACS Style

Alfuth, J.; Zadykowicz, B.; Sikorski, A.; Połoński, T.; Eichstaedt, K.; Olszewska, T. Effect of Aromatic System Expansion on Crystal Structures of 1,2,5-Thia- and 1,2,5-Selenadiazoles and Their Quaternary Salts: Synthesis, Structure, and Spectroscopic Properties. Materials 2020, 13, 4908. https://doi.org/10.3390/ma13214908

AMA Style

Alfuth J, Zadykowicz B, Sikorski A, Połoński T, Eichstaedt K, Olszewska T. Effect of Aromatic System Expansion on Crystal Structures of 1,2,5-Thia- and 1,2,5-Selenadiazoles and Their Quaternary Salts: Synthesis, Structure, and Spectroscopic Properties. Materials. 2020; 13(21):4908. https://doi.org/10.3390/ma13214908

Chicago/Turabian Style

Alfuth, Jan, Beata Zadykowicz, Artur Sikorski, Tadeusz Połoński, Katarzyna Eichstaedt, and Teresa Olszewska. 2020. "Effect of Aromatic System Expansion on Crystal Structures of 1,2,5-Thia- and 1,2,5-Selenadiazoles and Their Quaternary Salts: Synthesis, Structure, and Spectroscopic Properties" Materials 13, no. 21: 4908. https://doi.org/10.3390/ma13214908

APA Style

Alfuth, J., Zadykowicz, B., Sikorski, A., Połoński, T., Eichstaedt, K., & Olszewska, T. (2020). Effect of Aromatic System Expansion on Crystal Structures of 1,2,5-Thia- and 1,2,5-Selenadiazoles and Their Quaternary Salts: Synthesis, Structure, and Spectroscopic Properties. Materials, 13(21), 4908. https://doi.org/10.3390/ma13214908

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Effect of Aromatic System Expansion on Crystal Structures of 1,2,5-Thia- and 1,2,5-Selenadiazoles and Their Quaternary Salts: Synthesis, Structure, and Spectroscopic Properties

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