Hybrid Tuning in NHC Ligands: Synergistic Effects of BIAN π ‐Conjugation and Aryl σ ‐Modulation in Gold(I) Complexes

Hybrid Tuning in NHC Ligands: Synergistic Effects of BIAN π ‐Conjugation and Aryl σ ‐Modulation in Gold(I) Complexes Full article

Journal

Chemistry: A European Journal
ISSN: 0947-6539 , E-ISSN: 1521-3765

Output data

Year: 2025, Volume: 31, Number: 44, Article number : e202501647, Pages count : DOI: 10.1002/chem.202501647

Authors

Pankov Roman ¹ , Khanipova Aliya ¹ , Son Alexandra ² , Prima Darya ¹ , Kolesnikov Andrey ¹ , Ivanova Nina ¹ , Fakhrutdinov Artem ¹ , Minyaev Mikhail ¹ , Ananikov Valentine P. ¹

Affiliations

1	Zelinsky Institute of Organic Chemistry RAS: FGBUN Institut organiceskoj himii imeni N D Zelinskogo Rossijskoj akademii nauk Catalysis RUSSIAN FEDERATION
2	Kurnakov Institute of General and Inorganic Chemistry RAS: FGBUN Institut obsej i neorganiceskoj himii im. N S Kurnakova Rossijskoj akademii nauk Chemistry RUSSIAN FEDERATION

In this study, we explore extended design of metal–NHC complexes that relies on dual strategies for tuning ligand properties: (i) electronic modulation through π-extended frameworks such as bis(imino)acenaphthene (BIAN), and (ii) systematic aryl substitution to influence σ-donor strength and steric environment. We report the first integrated exploration of these two strategies on a unified ligand platform. A series of Au(I)/BIAN–NHCX complexes were synthesized by introducing electron-withdrawing substituents (X = F, Cl, Br, CF₃) at the ortho-, meta-, and para-positions of the N-aryl groups. This hybrid tuning approach allowed us to probe the synergistic and antagonistic effects arising from π–σ interplay across multiple dimensions. Each complex was thoroughly characterized with respect to synthetic yield, structural features (including X-ray structure and dynamics in solution), photophysical properties (UV-Vis and luminescence), catalytic performance in hydroamination of phenylacetylene, and cytotoxicity in HEK293T cells. Structure–property correlations revealed distinct cooperative and counteractive regimes depending on the substituent type and position. These findings demonstrate that combining orthogonal electronic control elements enables a more predictive and fine-grained design of NHC-based metal complexes, with future implications for catalysis, materials science, and biomedical applications.

Pankov R. , Khanipova A. , Son A. , Prima D. , Kolesnikov A. , Ivanova N. , Fakhrutdinov A. , Minyaev M. , Ananikov V.P.
Hybrid Tuning in NHC Ligands: Synergistic Effects of BIAN π ‐Conjugation and Aryl σ ‐Modulation in Gold(I) Complexes
Chemistry: A European Journal. 2025. V.31. N44. e202501647 . DOI: 10.1002/chem.202501647 OpenAlex

OpenAlex:

W4411469836

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