TY - JOUR

T1 - Crystal engineering with ambidentate thiocyanate: thiocyanate nitrogen as a halogen bond acceptor in platinum( ii ) complexes

AU - Антонова, Элина Вадимовна

AU - Кашина, Мария Владимировна

AU - Иванов, Даниил Михайлович

AU - Бокач, Надежда Арсеньевна

AU - Кинжалов, Михаил Андреевич

PY - 2025/10/8

Y1 - 2025/10/8

N2 - Halogen bonding (HaB) serves as a directional noncovalent interaction between electrophilic halogen donors and nucleophilic acceptors. This study demonstrates the unique role of thiocyanate nitrogen as a HaB acceptor in the supramolecular assembly of transition metal complexes. Pt(ii)–thiocyanate complexes featuring halogen-substituted aryl isocyanides [Pt(ppy)(SCN)(CNAr)] (ppy = 2-phenylpyridinato-C2,N; Ar = C6H3-2-I-4-Br 4, C6H3-2,4-I25, C6H3-2,4-Br26) were synthesized and fully characterized (HR ESIMS, IR, NMR, UV-vis, luminescence). Solution studies revealed a dynamic S/N-thiocyanate isomer equilibrium, while crystallization yielded exclusively S-coordinated solvates (4S·CHCl3, 5S·CHCl3, 6S·MeNO2). X-ray diffraction confirmed isomorphic structures stabilized by directional C–X⋯NCS (X = Br, I) HaBs, with the thiocyanate nitrogen acting as the preferred acceptor despite its coordination to platinum. Theoretical analyses (DFT, QTAIM, NCIplot, ELF, NBO) validated the σ-hole-driven interactions, revealing binding energies of 1.61–4.07 kcal mol−1. A Cambridge Structural Database survey underscores the rarity of such N⋯X contacts in metal–thiocyanate systems compared to prevalent S⋯X interactions. These findings establish thiocyanate nitrogen as an underutilized supramolecular synthon for crystal engineering of metal–organic materials.

AB - Halogen bonding (HaB) serves as a directional noncovalent interaction between electrophilic halogen donors and nucleophilic acceptors. This study demonstrates the unique role of thiocyanate nitrogen as a HaB acceptor in the supramolecular assembly of transition metal complexes. Pt(ii)–thiocyanate complexes featuring halogen-substituted aryl isocyanides [Pt(ppy)(SCN)(CNAr)] (ppy = 2-phenylpyridinato-C2,N; Ar = C6H3-2-I-4-Br 4, C6H3-2,4-I25, C6H3-2,4-Br26) were synthesized and fully characterized (HR ESIMS, IR, NMR, UV-vis, luminescence). Solution studies revealed a dynamic S/N-thiocyanate isomer equilibrium, while crystallization yielded exclusively S-coordinated solvates (4S·CHCl3, 5S·CHCl3, 6S·MeNO2). X-ray diffraction confirmed isomorphic structures stabilized by directional C–X⋯NCS (X = Br, I) HaBs, with the thiocyanate nitrogen acting as the preferred acceptor despite its coordination to platinum. Theoretical analyses (DFT, QTAIM, NCIplot, ELF, NBO) validated the σ-hole-driven interactions, revealing binding energies of 1.61–4.07 kcal mol−1. A Cambridge Structural Database survey underscores the rarity of such N⋯X contacts in metal–thiocyanate systems compared to prevalent S⋯X interactions. These findings establish thiocyanate nitrogen as an underutilized supramolecular synthon for crystal engineering of metal–organic materials.

UR - https://www.mendeley.com/catalogue/ad1a9261-cec4-341f-898a-eb5ad26ccf87/

U2 - 10.1039/d5ce00678c

DO - 10.1039/d5ce00678c

M3 - Article

VL - 27

SP - 6942

EP - 6948

JO - CrystEngComm

JF - CrystEngComm

SN - 1466-8033

IS - 42

ER -