TY - JOUR

T1 - Molecular complexes of iodine with pyrazine and 4,4’-bipyridine: Structure, bonding and thermal stability

AU - Давыдова, Елена Иоановна

AU - Антонова, Алёна Николаевна

AU - Шевченко, Анна Викторовна

AU - Спиридонова, Дарья Валерьевна

AU - Завгородний, Артем Сергеевич

AU - Дойников, Дмитрий Александрович

AU - Кондрашкина, Елизавета Игоревна

AU - Крюкова, Мария Александровна

AU - Помогаева, Анна Владимировна

AU - Тимошкин, Алексей Юрьевич

PY - 2025/5/1

Y1 - 2025/5/1

N2 - Results of the joint experimental and computational studies of structural features, bonding and thermodynamic properties of molecular complexes of iodine with bidentate nonchelated N-containing donors pyrazine and 4,4′-bipyridine are reported. Irrespective of the starting ratio of the components, complexes of 2:1 composition are predominantly formed in the solid state. Molecular structures of new molecular complex of I2 with pyrazine and a new polymorph of complex of 4,4′-bipyridine of 2:1 composition have been determined by single crystal structural analysis. In both complexes, ligand serves as bifunctional donor connecting two molecules of I2. All I[sbnd]N distances are shorter than the sum of van der Waals radii and the I-I-N angles are close to 180°. To reveal the stability of the complexes of different compositions and the nature of N[sbnd]I bond, the DFT computations were performed. Stability and volatility of compounds upon heating in vacuum were studied using static tensimetry method with membrane null-manometer. Thermodynamic characteristics of the complex dissociation processes were estimated.

AB - Results of the joint experimental and computational studies of structural features, bonding and thermodynamic properties of molecular complexes of iodine with bidentate nonchelated N-containing donors pyrazine and 4,4′-bipyridine are reported. Irrespective of the starting ratio of the components, complexes of 2:1 composition are predominantly formed in the solid state. Molecular structures of new molecular complex of I2 with pyrazine and a new polymorph of complex of 4,4′-bipyridine of 2:1 composition have been determined by single crystal structural analysis. In both complexes, ligand serves as bifunctional donor connecting two molecules of I2. All I[sbnd]N distances are shorter than the sum of van der Waals radii and the I-I-N angles are close to 180°. To reveal the stability of the complexes of different compositions and the nature of N[sbnd]I bond, the DFT computations were performed. Stability and volatility of compounds upon heating in vacuum were studied using static tensimetry method with membrane null-manometer. Thermodynamic characteristics of the complex dissociation processes were estimated.

KW - 4,4′-bipyridine

KW - Complexes

KW - DFT

KW - Iodine

KW - Pyrazine

KW - Structures

KW - Tensimetry

UR - https://www.mendeley.com/catalogue/5869147e-888c-33a6-aef1-cc7a3f0bacd9/

U2 - 10.1016/j.ica.2025.122564

DO - 10.1016/j.ica.2025.122564

M3 - Article

VL - 579

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

SN - 0020-1693

M1 - 122564

ER -