Effect of Ligand Chain Length for Tuning of Molecular Dimensionality and Magnetic Relaxation in Redox Active Cobalt(II) EDOT Complexes (EDOT=3,4‐Ethylenedioxythiophene)

Effect of Ligand Chain Length for Tuning of Molecular Dimensionality and Magnetic Relaxation in Redox Active Cobalt(II) EDOT Complexes (EDOT=3,4‐Ethylenedioxythiophene) Научная публикация

Журнал

Chemistry - An Asian Journal
ISSN: 1861-4728

Вых. Данные

Год: 2022, Том: 17, Номер: 16, Номер статьи : e202200404, Страниц : 12 DOI: 10.1002/asia.202200404

Авторы

Ghosh Subrata ¹ , Kamilya Sujit ¹ , Mehta Sakshi ¹ , Herchel Radovan ² , Kiskin Mikhail ³ , Veber Sergey ^4,5 , Fedin Matvey ^4,5 , Mondal Abhishake ¹

Организации

1	Solid State and Structural Chemistry Unit Indian Institute of Science Sir C. V. Raman Road 560012 Bangalore India
2	Department of Inorganic Chemistry Faculty of Science Palacký University CZ-771 46 Olomouc Czech Republic
3	N. S. Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences Leninsky Prosp. 31 119991 Moscow Russia
4	International Tomography Center of the Siberian Branch of the Russian Academy of Sciences Institutskaya Str. 3a 630090 Novosibirsk Russia
5	Novosibirsk State University Pirogova Str. 1 630090 Novosibirsk Russia

Four cobalt(II) complexes, [Co(L1)2(NCX)2(MeOH)2] (X=S (1), Se (2)) and {[Co(L2)2(NCX)2]}n (X=S (3), Se (4)) (L1=2,5-dipyridyl-3,4,–ethylenedioxylthiophene and L2=2,5-diethynylpyridinyl-3,4-ethylenedioxythiophene), were synthesized by incorporating ethylenedioxythiophene based redox-active luminescence ligands. All these complexes have been well characterized using single-crystal X-ray diffraction analyses, spectroscopic and magnetic investigations. Magneto-structural studies showed that 1 and 2 adopt a mononuclear structure with CoN4O2 octahedral coordination geometry while 3 and 4 have a 2D [4×4] rhombic grid coordination networks (CNs) where each cobalt(II) center is in a CoN6 octahedral coordination environment. Static magnetic measurements reveal that all four complexes displayed a high spin (HS) (S=3/2) state between 2 and 280 K which was further confirmed by X-band and Q-band EPR studies. Remarkably, along with the molecular dimensionality (0D and 2D) the modification in the axial coligands lead to a significant difference in the dynamic magnetic properties of the monomers and CNs at low temperatures. All complexes display slow magnetic relaxation behavior under an external dc magnetic field. For the complexes with NCS− as coligand observed higher energy barrier for spin reversal in comparison to the complexes with NCSe− as coligand, while mononuclear complex 1 exhibited a higher energy barrier than that of CN 3. Theoretical calculations at the DFT and CASSCF level of theory have been performed to get more insight into the electronic structure and magnetic properties of all four complexes.

Ghosh S. , Kamilya S. , Mehta S. , Herchel R. , Kiskin M. , Veber S. , Fedin M. , Mondal A.
Effect of Ligand Chain Length for Tuning of Molecular Dimensionality and Magnetic Relaxation in Redox Active Cobalt(II) EDOT Complexes (EDOT=3,4‐Ethylenedioxythiophene)
Chemistry - An Asian Journal. 2022. V.17. N16. e202200404 :1-12. DOI: 10.1002/asia.202200404 WOS Scopus OpenAlex

Поступила в редакцию:	18 апр. 2022 г.
Опубликована online:	15 июн. 2022 г.
Опубликована в печати:	15 авг. 2022 г.

Web of science:	WOS:000811250100001
Scopus:	2-s2.0-85131862044
OpenAlex:	W4281565653

БД	Цитирований
Scopus	5
Web of science	5