A series of red-emissive {Cu 4 I 6 } clusters have been synthesized from alkyl-tris(2-pyridyl)phosphonium halides, [R-PPy 3 ]Hal, and CuI. The size of the alkyl substituent (R) has a dramatic impact on the structure of the clusters assembled. [Me-PPy 3 ]I salt reacts with CuI (1 : 2) to give the ionic [Cu(Me-PPy 3 )I] 2 Cu 2 I 4 complex consisting of the scorpionate [Cu(N,N′,N′′-Me-PPy 3 )I] + cation. Under similar conditions, [Pr-PPy 3 ]I forms the zwitterionic [Cu 4 I 6 (Pr-TPP) 2 ] complex containing an unusual stepwise [Cu 4 I 6 ] cluster core. The use of [Bu-PPy 3 ]I or [Bn-PPy 3 ]I in this reaction leads to zwitterionic [Cu 4 I 6 (R-TPP) 2 ] complexes, in which a linear-shaped [Cu 4 I 6 ] 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 (λemmax = 620-650 nm) with short lifetimes (0.04-2.10 μs), which are assigned to the thermally activated delayed fluorescence (TADF) mixed with the cluster centered ( 3 CC) phosphorescence. The compounds synthesized are the first red-emitting representatives of the recently discovered family of zwitterionic CuI-based complexes (so-called “AIO” structures).

Язык оригиналаанглийский
Страницы (с-по)2328-2337
Число страниц10
ЖурналDalton Transactions
Номер выпуска7
СостояниеОпубликовано - 21 фев 2019

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