TY - JOUR

T1 - Remarkably short intermolecular Se···Se contacts in Ni(II) diselenophosphinates: interplay of electrostatic and dispersion

AU - Тупикина, Елена Юрьевна

AU - Давыдова, Мария

AU - Муллоярова, Валерия Вячеславовна

AU - Сухих, Таисия

AU - Самсоненко, Денис

AU - Толстой, Петр Михайлович

AU - Артемьев, Александр

PY - 2025

Y1 - 2025

N2 - We report the discovery of remarkably short intermolecular Se⋯Se contacts (3.242-3.751 Å) and a novel supramolecular Se/Se\Se/Se zigzag pattern in Ni(ii) diselenophosphinate complexes. The monoclinic polymorph of [Ni(Se2PPh2)2], along with [Ni(Se2PPh2)2(Pz)2] and the 1D polymer [Ni(Se2PPPh2)2(3,3′-bipy)]n, exhibit this zigzag pattern with one short (avg. 3.35 Å) and two longer (avg. 3.68 Å) Se⋯Se contacts between adjacent NiP2Se4 units. In contrast, the orthorhombic [Ni(Se2PPh2)2] and the 1D polymer [Ni(Se2PPPh2)2(4,4′-bipy)]n display chain-like intermolecular Se⋯Se contacts of about 3.51 Å. Employing a multifaceted approach, we elucidate the nature of the interactions, distinguishing between the electrostatic and dispersion contributions. Using theoretical methods (DFT-DKH for geometry optimization; electron density, ESP, ELF, and SAPT0 for analysis), we find that short Se⋯Se interactions (90% ∑rvdW(Se⋯Se)) are mainly attributed to electrostatic forces, typical of σ-hole interactions. Notably, we document an unprecedented Se⋯Se contact of 3.242 Å, which, to our knowledge, is the shortest proven non-covalent Se⋯Se interaction reported to date. This finding not only confirms the existence of Se⋯Se interactions, but also highlights their potential strength and importance in coordination chemistry, an aspect that has not been thoroughly explored in previous studies.

AB - We report the discovery of remarkably short intermolecular Se⋯Se contacts (3.242-3.751 Å) and a novel supramolecular Se/Se\Se/Se zigzag pattern in Ni(ii) diselenophosphinate complexes. The monoclinic polymorph of [Ni(Se2PPh2)2], along with [Ni(Se2PPh2)2(Pz)2] and the 1D polymer [Ni(Se2PPPh2)2(3,3′-bipy)]n, exhibit this zigzag pattern with one short (avg. 3.35 Å) and two longer (avg. 3.68 Å) Se⋯Se contacts between adjacent NiP2Se4 units. In contrast, the orthorhombic [Ni(Se2PPh2)2] and the 1D polymer [Ni(Se2PPPh2)2(4,4′-bipy)]n display chain-like intermolecular Se⋯Se contacts of about 3.51 Å. Employing a multifaceted approach, we elucidate the nature of the interactions, distinguishing between the electrostatic and dispersion contributions. Using theoretical methods (DFT-DKH for geometry optimization; electron density, ESP, ELF, and SAPT0 for analysis), we find that short Se⋯Se interactions (90% ∑rvdW(Se⋯Se)) are mainly attributed to electrostatic forces, typical of σ-hole interactions. Notably, we document an unprecedented Se⋯Se contact of 3.242 Å, which, to our knowledge, is the shortest proven non-covalent Se⋯Se interaction reported to date. This finding not only confirms the existence of Se⋯Se interactions, but also highlights their potential strength and importance in coordination chemistry, an aspect that has not been thoroughly explored in previous studies.

UR - https://www.mendeley.com/catalogue/9eca6856-c820-38c1-87e5-c744abf7e68b/

U2 - 10.1039/d4qi03204g

DO - 10.1039/d4qi03204g

M3 - Article

VL - 12

SP - 1568

EP - 1578

JO - Inorganic Chemistry Frontiers

JF - Inorganic Chemistry Frontiers

SN - 2052-1545

IS - 4

ER -