Novel applications of functionalized 2,1,3-benzothiadiazoles for coordination chemistry and crystal engineering

Novel applications of functionalized 2,1,3-benzothiadiazoles for coordination chemistry and crystal engineering Научная публикация

Журнал

RSC Advances
ISSN: 2046-2069

Вых. Данные

Год: 2014, Том: 4, Номер: 54, Страницы: 28309-28316 Страниц : DOI: 10.1039/c4ra03342f

Авторы

Bashirov Denis A. ^1,2 , Sukhikh Taisiya S. ¹ , Kuratieva Natalia V. ^1,2 , Chulanova Elena A. ^2,3 , Yushina Irina V. ¹ , Gritsan Nina P. ³ , Konchenko Sergey N. ^1,2 , Zibarev Andrey V. ^4,5,6

Организации

1	(Данные Web of science) Russian Acad Sci, Nikolaev Inst Inorgan Chem, Siberian Branch, Novosibirsk 630090, Russia
2	(Данные Web of science) Natl Res Univ Novosibirsk State Univ, Dept Nat Sci, Novosibirsk 630090, Russia
3	(Данные Web of science) Russian Acad Sci, Voevodsky Inst Chem Kinet & Combust, Siberian Branch, Novosibirsk 630090, Russia
4	(Данные Web of science) Russian Acad Sci, Siberian Branch, Vorozhtsov Inst Organ Chem, Novosibirsk 630090, Russia
5	(Данные Web of science) Natl Res Univ Novosibirsk State Univ, Dept Phys, Novosibirsk 630090, Russia
6	(Данные Web of science) Natl Res Univ Tomsk State Univ, Dept Chem, Tomsk 634050, Russia

Two novel applications of functionalized 2,1,3-benzothiadiazoles for metal coordination chemistry and crystal engineering of organic solids are presented. 4-Amino-2,1,3-benzothiadiazole (1) forms a 2 : 1 complex with ZnCl2 (complex 2) and a 1 : 1 complex with 4-nitro-2,1,3-benzothiadiazole (3) (complex 4). The structures of compounds 1-4 were confirmed by single-crystal X-ray diffraction and studied by UV-Vis and IR spectroscopy, and DFT and QTAIM calculations. Complex 2 is the first structurally defined Zn complex with 2,1,3-benzothiadiazole ligands. In this complex, both molecules 1 are coordinated to Zn only by amino groups, thus revealing a novel type of coordination of this ligand to the metal center. According to H-1 NMR data, complex 2 dissociates in CHCl3, THF or DMSO solutions. There are only a few examples of similar complexes, which are also considered to dissociate in solutions. In crystalline complex 4, molecules 1 and 3 form infinite alternating pi-stacks connected by lateral S...N interactions between the neighboring stacks. Intermolecular S...N interactions are also observed in the crystals of individual 1 and 3 but the packing motifs are different from those in 4. DFT calculations predict a small charge transfer (CT, similar to 0.02e at B97-D3 level) from 1 to 3 upon the formation of 4, which therefore is an unprecedented CT complex where both donor and acceptor moieties are the derivatives of the 2,1,3-benzothiadiazole ring system. This finding creates some new prospects for the crystal engineering of organic solids. Crystalline complex 4 is characterized by an intense CT absorption band with a maximum at similar to 550 nm. However, according to DFT and QTAIM calculations the complex is weakly bonded and its formation is not observed in CH2Cl2 solution with H-1 NMR and UV-Vis techniques.

Bashirov D.A. , Sukhikh T.S. , Kuratieva N.V. , Chulanova E.A. , Yushina I.V. , Gritsan N.P. , Konchenko S.N. , Zibarev A.V.
Novel applications of functionalized 2,1,3-benzothiadiazoles for coordination chemistry and crystal engineering
RSC Advances. 2014. V.4. N54. P.28309-28316. DOI: 10.1039/c4ra03342f WOS Scopus РИНЦ

Web of science	WOS:000339396000013
Scopus	2-s2.0-84903977798
РИНЦ	23958005
OpenAlex	W2094963614