Quantum dot (QD) sensitized triplet exciton generation has demonstrated promising applications in various fields such as photon up-conversion through triplet–triplet annihilation. However, how direct triplet energy transfer from the QD to the acceptor through Dexter energy transfer (DET) competes with other processes, including Förster resonance energy transfer (FRET) and charge transfer, remains poorly understood. Herein, the competition of these pathways for QD-sensitized triplet excited state generation in CdSe QD-modified boron dipyrromethene (BODIPY) complexes is studied using transient absorption spectroscopy. After excitation of the CdSe QD with 500 nm pulses, the BODIPY triplet excited state is generated through charge recombination in a charge separated intermediate state (QD−·–BODIPY+·). This intermediate state is populated either through FRET from the excited QD to BODIPY followed by electron transfer from the singlet excited state of BODIPY to the QD or through hole transfer from the excited QD to BODIPY. The triplet excited state generation efficiencies from the FRET and hole transfer pathways are estimated to be (6.18 ± 1.39)% and (13.5 ± 3.1)%, respectively. Compared to these indirect pathways, direct DET from the QD to the BODIPY triplet state is kinetically not competitive. These results demonstrate that sequential charge transfer can be an efficient pathway for triplet excited state generation in QD–acceptor complexes.
REFERENCES
1.
T. N.
Singh-Rachford
and F. N.
Castellano
, Coord. Chem. Rev.
254
(21-22
), 2560
–2573
(2010
).2.
N.
Yanai
and N.
Kimizuka
, Acc. Chem. Res.
50
(10
), 2487
–2495
(2017
).3.
T.
Serevičius
, R.
Komskis
, P.
Adomėnas
, O.
Adomėnienė
, G.
Kreiza
, V.
Jankauskas
, K.
Kazlauskas
, A.
Miasojedovas
, V.
Jankus
, A.
Monkman
, and S.
Juršėnas
, J. Phys. Chem. C
121
(15
), 8515
–8524
(2017
).4.
X. S.
Li
, S.
Kolemen
, J.
Yoon
, and E. U.
Akkaya
, Adv. Funct. Mater.
27
(5
), 1604053
(2017
).5.
P.
Majumdar
, R.
Nomula
, and J.
Zhao
, J. Mater. Chem. C
2
(30
), 5982
–5997
(2014
).6.
C.
Wohnhaas
, V.
Mailänder
, M.
Dröge
, M. A.
Filatov
, D.
Busko
, Y.
Avlasevich
, S.
Baluschev
, T.
Miteva
, K.
Landfester
, and A.
Turshatov
, Macromol. Biosci.
13
(10
), 1422
–1430
(2013
).7.
Y.
You
, Curr. Opin. Chem. Biol.
17
(4
), 699
–707
(2013
).8.
B.
Minaev
, G.
Baryshnikov
, and H.
Agren
, Phys. Chem. Chem. Phys.
16
(5
), 1719
–1758
(2014
).9.
X.-K.
Liu
, W.
Chen
, H. T.
Chandran
, J.
Qing
, Z.
Chen
, X.-H.
Zhang
, and C.-S.
Lee
, ACS Appl. Mater. Interfaces
8
(39
), 26135
–26142
(2016
).10.
J.
Zhao
, K.
Xu
, W.
Yang
, Z.
Wang
, and F.
Zhong
, Chem. Soc. Rev.
44
(24
), 8904
–8939
(2015
).11.
V.
Jankus
, P.
Data
, D.
Graves
, C.
McGuinness
, J.
Santos
, M. R.
Bryce
, F. B.
Dias
, and A. P.
Monkman
, Adv. Funct. Mater.
24
(39
), 6178
–6186
(2014
).12.
J.
Zhao
, K.
Chen
, Y.
Hou
, Y.
Che
, L.
Liu
, and D.
Jia
, Org. Biomol. Chem.
16
(20
), 3692
–3701
(2018
).13.
W.
Zhao
and F. N.
Castellano
, J. Phys. Chem. A
110
(40
), 11440
–11445
(2006
).14.
J.
Zhao
, W.
Wu
, J.
Sun
, and S.
Guo
, Chem. Soc. Rev.
42
(12
), 5323
–5351
(2013
).15.
D. V.
Kozlov
and F. N.
Castellano
, Chem. Commun.
29
(24
), 2860
–2861
(2004
).16.
J.
Zhao
, S.
Ji
, and H.
Guo
, RSC Adv.
1
(6
), 937
–950
(2011
).17.
D. L.
Dexter
, “A theory of sensitized luminescence in solid
,” J. Chem. Phys.
21
, 836
(1953
).18.
D. S.
Tyson
, C. A.
Bignozzi
, and F. N.
Castellano
, J. Am. Chem. Soc.
124
(17
), 4562
–4563
(2002
).19.
D.
Gust
, T. A.
Moore
, A. L.
Moore
, S.-J.
Lee
, E.
Bittersmann
, D. K.
Luttrull
, A. A.
Rehms
, J. M.
DeGraziano
, X. C.
Ma
, F.
Gao
, R. E.
Belford
, and T. T.
Trier
, Science
248
(4952
), 199
(1990
).20.
D.
Carbonera
, M.
Di Valentin
, C.
Corvaja
, G.
Agostini
, G.
Giacometti
, P. A.
Liddell
, D.
Kuciauskas
, A. L.
Moore
, T. A.
Moore
, and D.
Gust
, J. Am. Chem. Soc.
120
(18
), 4398
–4405
(1998
).21.
Z. E. X.
Dance
, Q.
Mi
, D. W.
McCamant
, M. J.
Ahrens
, M. A.
Ratner
, and M. R.
Wasielewski
, J. Phys. Chem. B
110
(50
), 25163
–25173
(2006
).22.
K.
Chen
, W.
Yang
, Z.
Wang
, A.
Iagatti
, L.
Bussotti
, P.
Foggi
, W.
Ji
, J.
Zhao
, and M.
Di Donato
, J. Phys. Chem. A
121
(40
), 7550
–7564
(2017
).23.
S. S.
Skourtis
, C.
Liu
, P.
Antoniou
, A. M.
Virshup
, and D. N.
Beratan
, Proc. Natl. Acad. Sci. U. S. A.
113
(29
), 8115
–8120
(2016
).24.
Z.-Q.
You
and C.-P.
Hsu
, Int. J. Quantum Chem.
114
(2
), 102
–115
(2014
).25.
Z.-Q.
You
, C.-P.
Hsu
, and G. R.
Fleming
, J. Chem. Phys.
124
(4
), 044506
(2006
).26.
S. H.
Lin
, Proc. R. Soc. London, Ser. A
335
(1600
), 51
(1973
).27.
G. L.
Closs
, M. D.
Johnson
, J. R.
Miller
, and P.
Piotrowiak
, J. Am. Chem. Soc.
111
(10
), 3751
–3753
(1989
).28.
J. E.
Subotnik
, J.
Vura-Weis
, A. J.
Sodt
, and M. A.
Ratner
, J. Phys. Chem. A
114
(33
), 8665
–8675
(2010
).29.
C.
Curutchet
and A. A.
Voityuk
, J. Phys. Chem. C
116
(42
), 22179
–22185
(2012
).30.
A.
Köhler
and H.
Bässler
, J. Mater. Chem.
21
(12
), 4003
–4011
(2011
).31.
C.
Mongin
, S.
Garakyaraghi
, N.
Razgoniaeva
, M.
Zamkov
, and F. N.
Castellano
, Science
351
(6271
), 369
–372
(2016
).32.
G. B.
Piland
, Z. Y.
Huang
, M. L.
Tang
, and C. J.
Bardeen
, J. Phys. Chem. C
120
(11
), 5883
–5889
(2016
).33.
X.
Li
, Z.
Huang
, R.
Zavala
, and M. L.
Tang
, J. Phys. Chem. Lett.
7
(11
), 1955
–1959
(2016
).34.
X.
Luo
, R.
Lai
, Y.
Li
, Y.
Han
, G.
Liang
, X.
Liu
, T.
Ding
, J.
Wang
, and K.
Wu
, J. Am. Chem. Soc.
141
(10
), 4186
–4190
(2019
).35.
D. J.
Norris
and M. G.
Bawendi
, J. Chem. Phys.
103
(13
), 5260
–5268
(1995
).36.
G. D.
Scholes
and G.
Rumbles
, Nat. Mater.
5
(9
), 683
–696
(2006
).37.
A. I.
Ekimov
, F.
Hache
, M. C.
Schanne-Klein
, D.
Ricard
, C.
Flytzanis
, I. A.
Kudryavtsev
, T. V.
Yazeva
, A. V.
Rodina
, and A. L.
Efros
, J. Opt. Soc. Am. B
10
(1
), 100
–107
(1993
).38.
W. W.
Yu
, L. H.
Qu
, W. Z.
Guo
, and X. G.
Peng
, Chem. Mater.
15
(14
), 2854
–2860
(2003
).39.
L.
Cademartiri
, E.
Montanari
, G.
Calestani
, A.
Migliori
, A.
Guagliardi
, and G. A.
Ozin
, J. Am. Chem. Soc.
128
(31
), 10337
–10346
(2006
).40.
H. M.
Zhu
and T. Q.
Lian
, Energy Environ. Sci.
5
(11
), 9406
–9418
(2012
).41.
H.
Zhu
, N.
Song
, and T.
Lian
, J. Am. Chem. Soc.
132
(42
), 15038
–15045
(2010
).42.
M. A.
Boles
, D.
Ling
, T.
Hyeon
, and D. V.
Talapin
, Nat. Mater.
15
(2
), 141
–153
(2016
).43.
S.
Kim
, B.
Fisher
, H.-J.
Eisler
, and M.
Bawendi
, J. Am. Chem. Soc.
125
(38
), 11466
–11467
(2003
).44.
M.
Wu
, D. N.
Congreve
, M. W. B.
Wilson
, J.
Jean
, N.
Geva
, M.
Welborn
, T.
Van Voorhis
, V.
Bulović
, M. G.
Bawendi
, and M. A.
Baldo
, Nat. Photonics
10
, 31
(2015
).45.
Z. Y.
Huang
, X.
Li
, B. D.
Yip
, J. M.
Rubalcava
, C. J.
Bardeen
, and M. L.
Tang
, Chem. Mater.
27
(21
), 7503
–7507
(2015
).46.
Z.
Huang
and M. L.
Tang
, J. Am. Chem. Soc.
139
(28
), 9412
–9418
(2017
).47.
Z.
Huang
, Z.
Xu
, M.
Mahboub
, X.
Li
, J. W.
Taylor
, W. H.
Harman
, T.
Lian
, and M. L.
Tang
, Angew. Chem., Int. Ed.
56
(52
), 16583
–16587
(2017
).48.
M.
Mahboub
, H.
Maghsoudiganjeh
, A. M.
Pham
, Z. Y.
Huang
, and M. L.
Tang
, Adv. Funct. Mater.
26
(33
), 6091
–6097
(2016
).49.
Z. Y.
Huang
, P.
Xia
, N.
Megerdich
, D. A.
Fishman
, V. I.
Vullev
, and M. L.
Tang
, ACS Photonics
5
(8
), 3089
–3096
(2018
).50.
Z.
Huang
, X.
Li
, M.
Mahboub
, K. M.
Hanson
, V. M.
Nichols
, H.
Le
, M. L.
Tang
, and C. J.
Bardeen
, Nano Lett.
15
(8
), 5552
–5557
(2015
).51.
J. A.
Bender
, E. K.
Raulerson
, X.
Li
, T.
Goldzak
, P.
Xia
, T.
Van Voorhis
, M. L.
Tang
, and S. T.
Roberts
, J. Am. Chem. Soc.
140
(24
), 7543
–7553
(2018
).52.
S.
Garakyaraghi
, C.
Mongin
, D. B.
Granger
, J. E.
Anthony
, and F. N.
Castellano
, J. Phys. Chem. Lett.
8
(7
), 1458
–1463
(2017
).53.
R. D.
Harcourt
, G. D.
Scholes
, and K. P.
Ghiggino
, J. Chem. Phys.
101
(12
), 10521
–10525
(1994
).54.
X.
Luo
, Y.
Han
, Z.
Chen
, Y.
Li
, G.
Liang
, X.
Liu
, T.
Ding
, C.
Nie
, M.
Wang
, F. N.
Castellano
, and K.
Wu
, Nat. Commun.
11
(1
), 28
(2020
).55.
C.
de Mello Donegá
, M.
Bode
, and A.
Meijerink
, Phys. Rev. B
74
(8
), 085320
(2006
).56.
D. J.
Weinberg
, S. M.
Dyar
, Z.
Khademi
, M.
Malicki
, S. R.
Marder
, M. R.
Wasielewski
, and E. A.
Weiss
, J. Am. Chem. Soc.
136
(41
), 14513
–14518
(2014
).57.
J.
Wang
, T.
Ding
, C.
Nie
, M.
Wang
, P.
Zhou
, and K.
Wu
, J. Am. Chem. Soc.
142
(10
), 4723
–4731
(2020
).58.
J. B.
Hoffman
, H.
Choi
, and P. V.
Kamat
, J. Phys. Chem. C
118
(32
), 18453
–18461
(2014
).59.
T.
Jin
, N.
Uhlikova
, Z.
Xu
, Y.
Zhu
, Y.
Huang
, E.
Egap
, and T.
Lian
, J. Chem. Phys.
151
(24
), 241101
(2019
).60.
J. E.
Huang
, Z. Q.
Huang
, S. Y.
Jin
, and T. Q.
Lian
, J. Phys. Chem. C
112
(49
), 19734
–19738
(2008
).61.
J.
Huang
, Z.
Huang
, Y.
Yang
, H.
Zhu
, and T.
Lian
, J. Am. Chem. Soc.
132
(13
), 4858
–4864
(2010
).62.
B.
Valeur
and N.
Berberan-Santos
, Molecular Fluorescence: Principles and Applications
, 2nd ed. (Wiley-VCH
, Weinheim
, 2012
), pp. 213
–261
.63.
Z.
Xu
, T.
Jin
, Y.
Huang
, K.
Mulla
, F. A.
Evangelista
, E.
Egap
, and T.
Lian
, Chem. Sci.
10
(24
), 6120
–6124
(2019
).64.
R. A.
Marcus
, Rev. Mod. Phys.
65
(3
), 599
–610
(1993
).65.
K.
Wu
, Y.
Du
, H.
Tang
, Z.
Chen
, and T.
Lian
, J. Am. Chem. Soc.
137
(32
), 10224
–10230
(2015
).66.
Y.
Han
, S.
He
, X.
Luo
, Y.
Li
, Z.
Chen
, W.
Kang
, X.
Wang
, and K.
Wu
, J. Am. Chem. Soc.
141
(33
), 13033
–13037
(2019
).© 2020 Author(s).
2020
Author(s)
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