Structural Resilience in Organic-Inorganic Stacked Assemblies: Sulfur-Mediated Self-Compensating Interaction and Metal Identity Masking in Group 10 Dithiocarbamate Cocrystals with Tetracyanobenzene

Structural Resilience in Organic-Inorganic Stacked Assemblies: Sulfur-Mediated Self-Compensating Interaction and Metal Identity Masking in Group 10 Dithiocarbamate Cocrystals with Tetracyanobenzene Научная публикация

Журнал

Inorganic Chemistry Frontiers
ISSN: 2052-1553 , E-ISSN: 2052-1545

Вых. Данные

Год: 2026, Том: 13, Номер: 1, Страницы: 232-245 Страниц : 14 DOI: 10.1039/D5QI01980J

Авторы

Zelenkov Lev E. ¹ , Baykov Sergey V. ² , Kuznetsov Maxim L. ³ , Sadykov Evgeny Kh. ⁴ , Nikul’shin Pavel V. ^5,6 , Ignatov Eugene V. ^2,7 , Bokach Nadezhda A. ² , Kukushkin Vadim Yu. ^2,7

Организации

1	Qingdao Innovation and Development Center, Harbin Engineering University, Qingdao 266000, Shandong, China
2	Institute of Chemistry, Saint Petersburg State University, Universitetskaya Nab. 7/9, 199034 Saint Petersburg, Russian Federation
3	Centro de Química Estrutural, Institute of Molecular Sciences, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal
4	Laboratory of Physical Chemistry of Condensed Matter, A. V. Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, Acad. Lavrentiev Av. 3, 630090 Novosibirsk, Russian Federation
5	A.N. Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences, 28 Vavilova St., 119991 Moscow, Russian Federation
6	N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences, 9, Lavrentiev Av., 630090 Novosibirsk, Russian Federation
7	Institute of Chemistry and Pharmaceutical Technologies, Altai State University, Lenin Av. 61, 656049 Barnaul, Russian Federation

This work investigates the relative influence of metal identity versus ligand environment in determining supramolecular architecture of stacked hybrid organic–inorganic systems. We demonstrate a sulfurmediated self-compensating mechanism that masks metal-specific electronic differences, enabling ligand-controlled assembly over conventional metal-directed organization. Through systematic investigation of group 10 metal dithiocarbamate cocrystals [M(S2CNR2)2] (M = Ni, Pd, Pt; R2 = alkyl) with 1,2,4,5tetracyanobenzene, we reveal structural resilience—identical parallel-displaced supramolecular architectures are maintained across the entire Ni–Pd–Pt triad despite fundamental differences in dz2-orbital nucleophilicity that typically govern such assemblies. This contradicts established principles where metal variation should produce distinctly different structural outcomes. Comprehensive quantum chemical analysis using QTAIM, IGM, ETS-NOCV, and energy decomposition methods reveals that S atoms from the dithiocarbamate ligands actively neutralize inherent metal-specific properties, creating electronically equivalent {MS4} building blocks. Despite different metals, remarkably consistent interaction energies (−40.6 to −42.8 kcal mol−1) and metal contributions (13.9–15.9%) demonstrate functional equivalence in the supramolecular recognition. Our study establishes ligand-mediated metal identity masking as a design principle for creating structurally predictable metal-involving materials regardless of metal center.

Zelenkov L.E. , Baykov S.V. , Kuznetsov M.L. , Sadykov E.K. , Nikul’shin P.V. , Ignatov E.V. , Bokach N.A. , Kukushkin V.Y.
Structural Resilience in Organic-Inorganic Stacked Assemblies: Sulfur-Mediated Self-Compensating Interaction and Metal Identity Masking in Group 10 Dithiocarbamate Cocrystals with Tetracyanobenzene
Inorganic Chemistry Frontiers. 2026. V.13. N1. P.232-245. DOI: 10.1039/D5QI01980J WOS Scopus

Поступила в редакцию:	26 сент. 2025 г.
Принята к публикации:	18 окт. 2025 г.
Опубликована online:	21 окт. 2025 г.
Опубликована в печати:	6 янв. 2026 г.

Web of science:	WOS:001600469200001
Scopus:	2-s2.0-105026445967

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