Synthesis, and structural and photophysical studies of mono- and dinuclear alkali metal 2,6-dibenzhydryl-4-methylphenolates

Synthesis, and structural and photophysical studies of mono- and dinuclear alkali metal 2,6-dibenzhydryl-4-methylphenolates Научная публикация

Журнал

New Journal of Chemistry
ISSN: 1369-9261 , E-ISSN: 1144-0546

Вых. Данные

Год: 2026, Том: 50, Страницы: 1261-1272 Страниц : 12 DOI: 10.1039/d5nj03734d

Авторы

Bardonov Daniil A. ^1,2 , Nasyrova Darina I. ^3,4 , Metlin Mikhail T. ^5,6 , Minyaev Mikhail E. ^1,4 , Taydakov Ilya V. ^1,6 , Roitershtein Dmitrii M. ^1,2

Организации

1	A.V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 29 Leninsky Prospect, Moscow 119991, Russian Federation
2	HSE University, 20 Myasnitskaya Str., Moscow 101000, Russian Federation
3	Moscow Institute of Physics and Technology (National Research University), 9 Institutskiy Per., Dolgoprudny, Moscow Region 141700, Russian Federation
4	N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 119991, 47 Leninsky Prospect, Russian Federation
5	Bauman Moscow State Technical University, 2-ya Baumanskaya str. 5/1, 105005 Moscow, Russian Federation
6	P.N. Lebedev Physical Institute of the Russian Academy of Sciences, Leninsky Prospekt 53, 119991 Moscow, Russian Federation

A series of dinuclear alkali metal 2,6-dibenzhydryl-4-methylphenolates [Ar*OM(THF)]2 (Ar* = 2,6-(Ph2CH)2-4-MeC6H2-; M1, M = Li, Na, K) were isolated from the reaction of metal bis(trimethylsilyl)amides with Ar*OH phenol in the THF medium. Recrystallization of M1 from pyridine yields [Ar*OM(py)]2 (M2). In addition to the aryloxide oxygens and solvent donor atoms, the metal cations in both M1 and M2 interact with the phenyl rings of the ligands. The hapticity of these interactions gradually changes from η2 (Li+) to η6 (K+). Treatment of Li1 with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me3tacn); Na1 with 12-crown-4 and 18-crown-6; and K1 with 18-crown-6 affords mononuclear complexes [Ar*OLi(Me3tacn)] (Li3), [Na(12-crown-4)2][OAr*] (Na4), [Ar*ONa(18-crown-6)] (Na6) and [Ar*OK(18-crown-6)] (K6), respectively. Ionic pairs [Na(12-crown-4)2][H(OAr*)2] (Na5) and [K(18-crown-6)(THF)2][H(OAr*)2] are formed upon interaction of Na4 and K6 with Ar*OH. The studied phenolates exhibit broadband luminescence spanning 370–800 nm, arising from the competition between π*–π transitions and emission from charge transfer states. In the solid state, mononuclear complexes display longer lifetimes due to suppression of non-radiative relaxation. This effect along with noticeable bathochromic shifts of the emission maxima may be attributed to formation of strong short hydrogen bonds.

Bardonov D.A. , Nasyrova D.I. , Metlin M.T. , Minyaev M.E. , Taydakov I.V. , Roitershtein D.M.
Synthesis, and structural and photophysical studies of mono- and dinuclear alkali metal 2,6-dibenzhydryl-4-methylphenolates
New Journal of Chemistry. 2026. V.50. P.1261-1272. DOI: 10.1039/d5nj03734d WOS Scopus OpenAlex

Поступила в редакцию:	19 сент. 2025 г.
Опубликована online:	8 дек. 2025 г.

≡ Web of science:	WOS:001644419900001
≡ Scopus:	2-s2.0-105025218293
≡ OpenAlex:	W4417121055