Research output: Contribution to journal › Article › peer-review
Alkyl-dependent self-assembly of the first red-emitting zwitterionic {Cu 4 I 6 } clusters from [alkyl-P(2-Py) 3 ] + salts and CuI : when size matters. / Artem'ev, Alexander V.; Pritchina, Elena A.; Rakhmanova, Marianna I. et al.
In: Dalton Transactions, Vol. 48, No. 7, 21.02.2019, p. 2328-2337.Research output: Contribution to journal › Article › peer-review
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TY - JOUR
T1 - Alkyl-dependent self-assembly of the first red-emitting zwitterionic {Cu 4 I 6 } clusters from [alkyl-P(2-Py) 3 ] + salts and CuI
T2 - when size matters
AU - Artem'ev, Alexander V.
AU - Pritchina, Elena A.
AU - Rakhmanova, Marianna I.
AU - Gritsan, Nina P.
AU - Bagryanskaya, Irina Yu
AU - Malysheva, Svetlana F.
AU - Belogorlova, Nataliya A.
PY - 2019/2/21
Y1 - 2019/2/21
N2 - 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).
AB - 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).
KW - ZETA VALENCE QUALITY
KW - THERMOCHROMIC-LUMINESCENCE
KW - BASIS-SETS
KW - COMPLEXES
KW - PHOTOPHYSICS
KW - PHOSPHORS
KW - LIGANDS
KW - FAMILY
UR - http://www.scopus.com/inward/record.url?scp=85061404117&partnerID=8YFLogxK
U2 - 10.1039/c8dt04328k
DO - 10.1039/c8dt04328k
M3 - Article
C2 - 30604786
AN - SCOPUS:85061404117
VL - 48
SP - 2328
EP - 2337
JO - Dalton Transactions
JF - Dalton Transactions
SN - 1477-9226
IS - 7
ER -
ID: 18560767