Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
New Charge-Transfer Complexes with 1,2,5-Thiadiazoles as Both Electron Acceptors and Donors Featuring an Unprecedented Addition Reaction. / Chulanova, Elena A.; Pritchina, Elena A.; Malaspina, Lorraine A. и др.
в: Chemistry - A European Journal, Том 23, № 4, 18.01.2017, стр. 852-864.Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
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TY - JOUR
T1 - New Charge-Transfer Complexes with 1,2,5-Thiadiazoles as Both Electron Acceptors and Donors Featuring an Unprecedented Addition Reaction
AU - Chulanova, Elena A.
AU - Pritchina, Elena A.
AU - Malaspina, Lorraine A.
AU - Grabowsky, Simon
AU - Mostaghimi, Farzin
AU - Beckmann, Jens
AU - Bagryanskaya, Irina Yu
AU - Shakhova, Margarita V.
AU - Konstantinova, Lidia S.
AU - Rakitin, Oleg A.
AU - Gritsan, Nina P.
AU - Zibarev, Andrey V.
N1 - Publisher Copyright: © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2017/1/18
Y1 - 2017/1/18
N2 - The design and synthesis of novel charge-transfer (CT) complexes are of interest for fundamental chemistry and applications to materials science. In addition to the recently described first CT complex with both electron acceptor (A) and donor (D) groups belonging to the 1,2,5-thiadiazole series (1; A: 4-nitro-2,1,3-benzothiadiazole; D: 4-amino-2,1,3-benzothiadiazole), herein novel CT complexes 2 and 3 with 1,2,5-thiadiazoles as both A (4,6-dinitro-2,1,3-benzothiadiazole and [1,2,5]thiadiazolo[3,4-c][1,2,5]thiadiazole) and D (4-amino-2,1,3-benzothiadiazole) were synthesized. The series is completed by complex 4 with [1,2,5]thiadiazolo[3,4-c][1,2,5]thiadiazole as A and phenoxatellurine as D. Structures of complexes 2–4 were characterized by single-crystal X-ray diffraction (XRD), as well as solution and solid-state UV/Vis spectroscopy. Thermodynamics of their formation were obtained by density functional theory (DFT) calculations, their bonding situations were analyzed by quantum theory of atoms in molecules (QTAIM) calculations and dimer model energies of interactions quantified in the framework of the Hirshfeld surface (HS) analysis. With DFT calculations, the largest value of CT between D and A was found for complex 2, with 0.027 e in the XRD structure and 0.150 e in the optimized structure in MeCN. In the UV/Vis spectra, the λmax of the CT bands of 2–4 varied in the range λ=517–705 nm. Model energy calculations for 1–4 revealed the importance of both dispersion interactions and hydrogen bonding between D and A as contributors to CT in the crystalline state. In an attempt to enlarge the CT value with bis[1,2,5-thiadiazolo][3,4-b;3′,4′-e]pyrazine as A and 4-amino-2,1,3-benzoselenadiazole as D, an unprecedented 1:1 addition reaction was observed upon formation of a C−N bond between atom C7 of D and pyrazine atom N4 of A, accompanied by hydrogen atom transfer from C7 to another pyrazine atom N8 (compound 5). According to DFT calculations, the reaction is a multistep process featuring diradical intermediates and hydrogen atom intramolecular migration over four positions. Molecular and crystal structures of 5 (solvate with toluene) were elucidated by XRD and the crystal structure revealed a rather unusual porous framework.
AB - The design and synthesis of novel charge-transfer (CT) complexes are of interest for fundamental chemistry and applications to materials science. In addition to the recently described first CT complex with both electron acceptor (A) and donor (D) groups belonging to the 1,2,5-thiadiazole series (1; A: 4-nitro-2,1,3-benzothiadiazole; D: 4-amino-2,1,3-benzothiadiazole), herein novel CT complexes 2 and 3 with 1,2,5-thiadiazoles as both A (4,6-dinitro-2,1,3-benzothiadiazole and [1,2,5]thiadiazolo[3,4-c][1,2,5]thiadiazole) and D (4-amino-2,1,3-benzothiadiazole) were synthesized. The series is completed by complex 4 with [1,2,5]thiadiazolo[3,4-c][1,2,5]thiadiazole as A and phenoxatellurine as D. Structures of complexes 2–4 were characterized by single-crystal X-ray diffraction (XRD), as well as solution and solid-state UV/Vis spectroscopy. Thermodynamics of their formation were obtained by density functional theory (DFT) calculations, their bonding situations were analyzed by quantum theory of atoms in molecules (QTAIM) calculations and dimer model energies of interactions quantified in the framework of the Hirshfeld surface (HS) analysis. With DFT calculations, the largest value of CT between D and A was found for complex 2, with 0.027 e in the XRD structure and 0.150 e in the optimized structure in MeCN. In the UV/Vis spectra, the λmax of the CT bands of 2–4 varied in the range λ=517–705 nm. Model energy calculations for 1–4 revealed the importance of both dispersion interactions and hydrogen bonding between D and A as contributors to CT in the crystalline state. In an attempt to enlarge the CT value with bis[1,2,5-thiadiazolo][3,4-b;3′,4′-e]pyrazine as A and 4-amino-2,1,3-benzoselenadiazole as D, an unprecedented 1:1 addition reaction was observed upon formation of a C−N bond between atom C7 of D and pyrazine atom N4 of A, accompanied by hydrogen atom transfer from C7 to another pyrazine atom N8 (compound 5). According to DFT calculations, the reaction is a multistep process featuring diradical intermediates and hydrogen atom intramolecular migration over four positions. Molecular and crystal structures of 5 (solvate with toluene) were elucidated by XRD and the crystal structure revealed a rather unusual porous framework.
KW - chalcogens
KW - charge transfer
KW - donor–acceptor systems
KW - quantum chemistry
KW - X-ray diffraction
KW - HETEROSPIN S-1
KW - ORGANIC SOLAR-CELLS
KW - X-RAY-STRUCTURE
KW - CRYSTAL-STRUCTURES
KW - EXCITED-STATES
KW - donor-acceptor systems
KW - BASIS-SETS
KW - DENSITY-FUNCTIONAL THEORY
KW - 1,2,5-CHALCOGENADIAZOLE DERIVATIVES
KW - RADICAL-ANION
KW - EXPLORING INTERMOLECULAR INTERACTIONS
UR - http://www.scopus.com/inward/record.url?scp=85006710509&partnerID=8YFLogxK
U2 - 10.1002/chem.201604121
DO - 10.1002/chem.201604121
M3 - Article
C2 - 27958639
AN - SCOPUS:85006710509
VL - 23
SP - 852
EP - 864
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
SN - 0947-6539
IS - 4
ER -
ID: 9064280