Alkyl-dependent self-assembly of the first red-emitting zwitterionic {Cu4I6} clusters from [alkyl-P(2-Py)(3)](+) salts and CuI: when size matters

Alkyl-dependent self-assembly of the first red-emitting zwitterionic {Cu4I6} clusters from [alkyl-P(2-Py)(3)](+) salts and CuI: when size matters Научная публикация

Журнал

Dalton Transactions
ISSN: 1477-9226 , E-ISSN: 1477-9234

Вых. Данные

Год: 2019, Том: 48, Номер: 7, Страницы: 2328-2337 Страниц : 10 DOI: 10.1039/c8dt04328k

Авторы

Artem'ev Alexander V. ^1,2 , Pritchina Elena A. ^2,3 , Rakhmanova Marianna I. ^1,2 , Gritsan Nina P. ^2,3 , Bagryanskaya Irina Yu. ^2,4 , Malysheva Svetlana F. ⁵ , Belogorlova Nataliya A. ⁵

Организации

1	(Данные Web of science) Russian Acad Sci, Siberian Branch, Nikolaev Inst Inorgan Chem, 3 Akad Lavrentiev Ave, Novosibirsk 630090, Russia
2	(Данные Web of science) Novosibirsk State Univ, Natl Res Univ, 2 Pirogova Str, Novosibirsk 630090, Russia
3	(Данные Web of science) Voevodsky Inst Chem Kinet & Combust, Inst Skaya Str 3, Novosibirsk 630090, Russia
4	(Данные Web of science) Russian Acad Sci, Siberian Branch, NN Vorozhtsov Novosibirsk Inst Organ Chem, 9 Akad Lavrentiev Ave, Novosibirsk 630090, Russia
5	(Данные Web of science) Russian Acad Sci, Siberian Branch, AE Favorsky Irkutsk Inst Chem, 1 Favorsky Str, Irkutsk 664033, Russia

A series of red-emissive {Cu4I6} clusters have been synthesized from alkyl-tris(2-pyridyl)phosphonium halides, [R-PPy3]Hal, and CuI. The size of the alkyl substituent (R) has a dramatic impact on the structure of the clusters assembled. [Me-PPy3]I salt reacts with CuI (1:2) to give the ionic [Cu(Me-PPy3)I](2)Cu2I4 complex consisting of the scorpionate [Cu(N,N,N-Me-PPy3)I](+) cation. Under similar conditions, [Pr-PPy3]I forms the zwitterionic [Cu4I6(Pr-TPP)(2)] complex containing an unusual stepwise [Cu4I6] cluster core. The use of [Bu-PPy3]I or [Bn-PPy3]I in this reaction leads to zwitterionic [Cu4I6(R-TPP)(2)] complexes, in which a linear-shaped [Cu4I6] module appears. Photophysical studies supported by TD-DFT computations have revealed that the title complexes in the solid state at 298 K exhibit a red photoluminescence (emmax = 620-650 nm) with short lifetimes (0.04-2.10 s), which are assigned to the thermally activated delayed fluorescence (TADF) mixed with the cluster centered ((CC)-C-3) phosphorescence. The compounds synthesized are the first red-emitting representatives of the recently discovered family of zwitterionic CuI-based complexes (so-called AIO structures).

Artem'ev A.V. , Pritchina E.A. , Rakhmanova M.I. , Gritsan N.P. , Bagryanskaya I.Y. , Malysheva S.F. , Belogorlova N.A.
Alkyl-dependent self-assembly of the first red-emitting zwitterionic {Cu4I6} clusters from [alkyl-P(2-Py)(3)](+) salts and CuI: when size matters
Dalton Transactions. 2019. V.48. N7. P.2328-2337. DOI: 10.1039/c8dt04328k WOS Scopus РИНЦ

Web of science	WOS:000459626400008
Scopus	2-s2.0-85061404117
РИНЦ	38656625
OpenAlex	W2904028464