Tunable Multicolor Phosphorescence of Crystalline Polymeric Complex Salts with Metallophilic Backbones

Article abstract of DOI:10.1002/anie.201803965

A total of 35 [Au(NHC)₂][MX₂] (NHC=N-heterocyclic carbene; M=Au or Cu; X=halide, cyanide or arylacetylide) complex salts were synthesized by co-precipitation of [Au(NHC)₂]⁺ cations and [MX₂]^? anions. These salts contain crystallographically determined polymeric Au???Au or Au???Cu interactions and are highly phosphorescent with quantum yields up to unity and emission color tunable in the entire visible regions. The nature of the emissive excited states is generally assigned to ligand (anion)-to-ligand (cation) charge-transfer transitions assisted by d¹⁰???d¹⁰ metallophilicity. The emission properties can be further tuned by controlled triple-component co-crystallization or by epitaxial growth. Correct recipes for white light-emitting phosphors with quantum yields higher than 70 % have been achieved by screening the combinatorial pool.

Full text of DOI:10.1002/anie.201803965

A Journal of the Gesellschaft Deutscher Chemiker
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Accepted Article
Title: Tunable Multicolor Phosphorescence of Crystalline Polymeric
Complex Salts with Metallophilic Backbones
Authors: Wei Lu, Qi Liu, Mo Xie, Xiaoyong Chang, Shuang Cao, Chao
Zou, Wen-Fu Fu, Chi-Ming Che, and Yong Chen
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201803965
Angew. Chem. 10.1002/ange.201803965
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10.1002/anie.201803965
Angewandte Chemie International Edition
COMMUNICATION
Tunable Multicolor Phosphorescence of Crystalline Polymeric
Complex Salts with Metallophilic Backbones
Qi Liu,[a,b] Mo Xie,[b] Xiaoyong Chang,[b] Shuang Cao,[a] Chao Zou,[b] Wen-Fu Fu,[a] Chi-Ming Che,[c]
Yong Chen,*[a] and Wei Lu*[b]
attracted much research endeavor due to the energies of the low-
lying excited states highly sensitive to the extent of the
metallophilicity.[11-13] Some polymeric complexes salts with
extended d10∙∙∙d10 metallophilic mainchains have scattered in the
literature,[14] but the luminescent properties remained elusive until
we serendipitously spotted two blue-emitting polymeric double
salts [Au(NHC)2][Au(CN)2] (NHC = N-heterocyclic carbene) (C1-
A1 and C2-A1, Figure 1a) in 2014.[15] Herein we report rational
syntheses of the phosphorescent [Au(NHC)2][MX2] (M = Au or Cu;
X = halide, cyanide or arylacetylide) complex salts containing
crystallographically determined polymeric Au∙∙∙Au and/or Au∙∙∙Cu
interactions, and with emission color extensively tunable in the
entire visible regions and into white by triple-component co-
crystallization or by epitaxial growth.
Abstract: A total of 35 [Au(NHC)2][MX2] (NHC = N-heterocyclic
carbene; M = Au or Cu; X = halide, cyanide or arylacetylide) complex
salts were synthesized by co-precipitation of [Au(NHC)2]+ cations and
[MX2] anions. These salts contain crystallographically determined
polymeric Au∙∙∙Au or Au∙∙∙Cu interactions and are highly
phosphorescent with quantum yields up to unity and emission color
tunable in the entire visible regions. The nature of the emissive excited
states is generally assigned to ligand (anion)-to-ligand (cation)
charge-transfer transitions assisted by d10∙∙∙d10 metallophilicity. The
emission properties can be further tuned by controlled triple-
component co-crystallization or by epitaxial growth. Correct recipes
for white light-emitting phosphors with quantum yields higher than 70%
have been achieved by screening the combinatorial pool.
a)
Phosphorescent metal complexes with emission color chemically
tunable in the entire visible regions meanwhile maintaining high
emission quantum yields are desirable for light-emitting devices,[1]
photon upconverting[2] and chemosensing[3] applications. White
light-emitting materials are particularly interesting and are
promising for cost-effective solid-state lighting technology.[4] One
solution to this issue is to incorporate multi-color emitting
phosphors to the main chain of an organic polymers[5] or into
crystalline metal-organic frameworks.[6] Single multi-functioning
emitters involving more than one emissive excited states could be
more effective.[7] For instance, square-planar Pt(II)[8] and linear-
coordination Au(I) complexes[9] have been employed as a single
dopant for white light-emitting solid on account of their dual
emissions originating from both monomers and excimers. In this
context, developments of new types of energy-efficient and
single-phase white light-emitting phosphors are still of immense
importance.
b)
b
a
c
Metal-organic complex salts consist of alternating cations and
anions arranged into one-dimensional chains running through the
crystals/supramolecular polymers.[10] In this context, square-
planar Pt(II) featuring metallophillic d8∙∙∙d8 interactions have
3.174 Å
Au
N
C
Figure 1. (a) Chemical structures of four cationic (C) and fourteen anionic (A)
precursors for the preparation of polymeric complex salts. PPN
=
[a] Q. Liu, Dr. S. Cao, Prof. Dr. W.-F. Fu, Prof. Dr. Y. Chen
Technical Institute of Physics and Chemistry & University of Chinese
Academy of Sciences
bis(triphenylphosphine)iminium, nBu4N = tetra(n-butyl) ammonium, 18C6 = 18-
crown-6; (b) Packing diagrams of the single crystal structures of C3-A8. Note
that the 3-methylpyridylacetylide ligands are heavily disordered and only one
orientation is shown here for clarity.
Chinese Academy of Sciences
Beijing 100190, P. R. China
E-mail: chenyong@mail.ipc.ac.cn
[b] Q. Liu, Dr. M. Xie, Dr. X.-Y. Chang, Dr. C. Zou. Prof. Dr. W. Lu
Department of Chemistry

We started with four [Au(NHC)2]+Y (Y = Cl or PF6 ) and
fourteen Z+[MX2] (Z = K+, PPN+, nBu4N+ or [18C6]-K+) precursors
(Figure 1a). The NHC ligands were judiciously selected as 1,3-
dimethylimidazol-2-ylidene, 1,3-dimethylbenzimidazol-2-ylidene,
1,3-dimethylimidazo[4,5-b]pyrazin-2-ylidene, and 2,4-dimethyl-
1,2,4-triazol-3-ylidene for C1C4, respectively, with C3 the most
electron-deficient. The metal ions in the [MX2] anion were Au(I)
(A1A4 and A8A13)[16] and Cu(I) (A5C7) due to the well-
documented d10 metal chemistry. The X ligands of the [MX2]
anion were chosen from synthetically available halides (Cl, Br,
South University of Science and Technology of China
Shenzhen, Guangdong 518055, P. R. China
E-mail: luw@sustc.edu.cn
[c] Prof. Dr. C. M. Che
The University of Hong Kong
Pokfulam Road, Hong Kong SAR, P. R. China
Supporting information for this article is given via a link at the end of
the document.
This article is protected by copyright. All rights reserved.

10.1002/anie.201803965
Angewandte Chemie International Edition
COMMUNICATION
I, A2A7), pseudo-halides (CN, A1) and arylacetylides
(A8A14). A total of 35 [Au(NHC)2][MX2] complex double salts
were prepared by co-precipitation processes from the chosen
cationic and anionic precursors in water or in acetonitrile. The
deposited solids were recrystallized to give double salts in
reasonably high yields. The cations and anions in the double salts
have been confirmed with high-resolution ESI-MS in positive and
negative mode, respectively.
emission quantum yields span from 10% for C3-A10 to 99% for
C1-A5 and C2-A5.
The emission energies of the [Au(NHC)2][AuX2] complex salts
are fine-tunable by varying the electronic properties of ligands on
both cations and anions. Structure-property trends could be
recognized by summarizing the emission data for the 35 complex
salts. (1) If the anion is fixed, the emission energy of the complex
salt red-shifts with more electron withdrawing NHC ligands on the
cations. For example, the emission maximum is 450, 470, 493
and 555 nm for C1-A1, C2-A1, C4-A1 and C3-A1, respectively
(Figure S20). The complex salt with C3 as cation and thus the
most electron-deficient 1,3-dimethylimidazo[4,5-b]pyrazin-2-
ylidene ligand showed lowest-energy emission in the series
containing the same anion. (2) If the cation is fixed, the emission
energy of the complex salt red-shifts with more electron donating
ligands on the anion series of [AuX2] but remains constant for the
anion series of [CuX2]. For example, the emission maximum is
469, 540, 558, and 570 for C2-A1 (X = CN), C2-A2 (X = Cl), C2-
A3 (X = Br), and C2-A4 (X = I), respectively (Figure S16). Anions
containing -donating arylacetylides generally red-shift the
emission energies of the double salts. (3) The [Au(NHC)2][CuCl2]
series of double salts containing Au∙∙∙Cu interactions achieve the
highest emission quantum yields close to unity.
Ten single crystal structures of the double salts have been
solved with X-ray crystallography (Table S1).[17] As
a
representative example, the crystal packing diagram of C3-A8 (in
C2/m space group) is shown in Figure 1b to confirm the one-
dimensional packing with alternating cations and anions
connected by infinite d10∙∙∙d10 metallophillic interactions in the
solid state. The intermetal Au∙∙∙Au distances in C3-A8 is uniform
to be 3.174 Å and the AuAuAu angle is 180o. The Au∙∙∙Au and
Au∙∙∙Cu distances found in the solved single crystal structures of
the ten double salts are 3.1823.384 Å and 3.3733.398 Å,
respectively, which are comparable with those d10∙∙∙d10
metallophillic interactions reported in the literature.[18] The phase
homogeneity of the bulky solid samples has been confirmed by
comparing the patterns recorded with powder X-ray diffraction
(PXRD) and those simulated with the single crystal data (Figure
S1S5 and S6S14).
a)
a)
A1
A2
A3
A4
A5
A6
A7
C1
C2
C2-A1
HOMO
HOMO
HOMO
LUMO
LUMO
LUMO
b)
c)
C3
C4
C2-A1-C2-A1
A8
A9
A10
A11
A12
A13
A14
C3
1.2
1.0
0.8
0.6
0.4
0.2
0.0
b)
C2-A1 C4-A6 C2-A4 C3-A5 C3-A12 C3-A14
C2-A1-C2-A1-C2-A1
Figure 3. TD-DFT calculated frontier orbitals for dinuclear (a), tetranulcear (b),
and hexanuclear (c) oligomers of C2-A1.
To shed light on the nature of the lower-energy transitions of
the complex double salts, we performed TD-DFT calculations on
oligomeric segments of C2-A1 with parameters abstracted from
the crystal structures and the resulted frontier orbitals are
depicted in Figure 3a-c. The HOMO of the dinuclear moiety is
localized on the dicyanoaurate anions with contribution from the
d* orbital of the Au∙∙∙Au weak bonding and the LUMO is localized
on the [Au(NHC)]+ cations. With the size of the segment extending
to tetranuclear and hexanuclear, the HOMOs are populated on
the anions and the Au∙∙∙Au weak bonding on one end of the
oligomers, and the LUMOs are localized on the cations on the
other end. Low-lying electronic transitions can thus be largely
described as ligand (anion)-to-ligand (cation) charge transfer
mixing with d*-p transition of the Au∙∙∙Au interactions, that is, a
mixture of LL’CT and MMCT. This assignment is supportive to the
results obtained from emission spectra in which electron-rich
ligands on anions and/or electron-deficient ligands on cations red-
shift the emission energies of the complex salts.
400 500 600 700 800 900 1000 1100
 / nm
Figure 2. (a) The images of the 35 complex salts dispersed in water or
acetonitrile observed under a 365 UV lamp; (b) Normalized solid-state emission
spectra of selected complex salts showing the multi-colors.
The as-prepared complex salts are emissive in the solid state.
Figure 2a lists all the 35 complex salts dispersed in water or
acetonitrile under a 365 nm UV lamp, and representative emission
spectra are depicted in Figure 2b to showcase the multi-color
emissions spanning the entire visible region and extending into
the near-infrared region. The full datasheet (Table S2) and
spectra (Figure S15S25) for all the complex salts are provided
in the Supporting Information. In general, the emission maxima
span from 448 nm for C1-A1 to 785 nm for C3-A14, emission
lifetimes span from 0.1 s for C3-A13 to 7.1 s for C1-A2, and
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10.1002/anie.201803965
Angewandte Chemie International Edition
COMMUNICATION
With a combinatorial pool of complex double salts in hands, we
conceived to combine two phosphors with different emission
colors to realize multi-color emission in a complex triple salt. Solid
samples of double salts C2-A1 and C2-A4 phosphoresce at peak
maximum of 469 and 570 nm, respectively, and these two salts
are essentially isostructural in both crystal lattice and molecular
packing,[19] as determined with single crystal X-ray
crystallography (Figure 4a and 4b). We thus co-crystalized C2, A1
and A4 with the molar ratio of C2:A1:A4 of 2:1:1 and successfully
obtained a single crystal of the triple salts of C2-A1/A4 (A1:A4 =
1:1) suitable for X-ray structure measurements.[17] The
dicyanoaurate and diiodoaurate anions have been determined to
be 50% occupancy each in the crystal lattice (Figure 4c). The
incorporation of the diiodoaurate (A4) anion into C2-A1 double
salt doesn’t alter the crystalline phase. Crystals C2-A1, C2-A4
and C2-A1/A4 crystallize into P21/c space group and the one-
dimensional infinite metallophillic backbones run along c-axis with
a uniform intermetal distance of 3.283, 3.384, and 3.337 Å,
respectively. We have been able to record the emission spectrum
of each of the single crystals with a fluorimeter coupled to a
microscope. The C2-A1/A4 (A1:A4 = 1:1) single crystal show dual
emission bands at 586/652 nm. The emerging 650 nm band is
much red-shifted from 469 nm for C2-A1 and 570 nm for C2-A4
single crystals (Figure 3d).
The nature of the lower-energy 652 nm emission was studied
by performing TD-DFT calculations on the two sequential
repeating units in C2-A1, C2-A4 and C2-A1/A4 with parameters
abstracted from the crystal structures (Figure 4e). The
replacement of dicyanoaurate (A1) in C2-A1-C2-A1 by
diiodoaurate (A4) in C2-A4-C2-A4 raises the energies of both the
HOMO and LUMO, presumably due to stronger -donating and
weaker -accepting capability of the iodide ligand when compared
with that of cyanide. In the models of C2-A1-C2-A4, the energy
levels of the HOMO-2 and LUMO involved in the low-energy
transitions are similar with that of HOMO-2 of C2-A4-C2-A4 and
LUMO of C2-A1-C2-A1, respectively, giving rise to a narrower
energy gap. The energy-gap of C2-A1-C2-A1, C2-A4-C2-A4, and
C2-A1-C2-A4 is calculated to be at about 417, 438, 414, and 445
nm, respectively. Thus, when the calculated segments coexist in
the structure of C2-A1/A4, the lowest-energy electronic transition
would be red-shifted from those of the pure C2-A1 and C2-A4
phases.
a)
b)
Co-crystallization
C2
A1, A4
C2-A1-C2-A1-C2-A1-C2-A1
C2-A4-C2-A1-C2-A1-C2-A1
C2-A1-C2-A1-C2-A4-C2-A1
C2-A4-C2-A1-C2-A1-C2-A1
a)
b)
60 m
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0
1.2
A1:A4
199:1
198:2
196:4
192:8
188:12
c)
Au
Au
N
C
I
Monitored @ 470 nm
Monitored @ 670 nm
N
C
1.0
0.8
0.6
0.4
0.2
0.0
C2-A1
C2-A4
d)
c)
1.0
0.8
0.6
0.4
0.2
0.0
Au
N
C
I
300
350
400
450 400
500
600
 / nm
700
800
 / nm
Epitaxial Growth
A4
C2-A1/A4
400
500
600
 / nm
700
800
d)
e)
A1:A4 = 1:1
e)
LUMO
C2-A1
LUMO
LUMO
LUMO
3.16eV
C2-A4-C2-A4-C2-A4-C2-A4
C2-A4-C2-A1-C2-A1-C2-A4
C2-A4-C2-A1-C2-A1-C2-A4
C2-A4-C2-A4-C2-A4-C2-A4
3.11eV
3.37eV
100 m
3.33eV
1.2
HOMO
f)
2.0
1.5
1.0
0.5
0.0
Monitored @ 470 nm
Monitored @ 570 nm
Excited @ nm
340
HOMO
HOMO-2
1.0
0.8
0.6
0.4
0.2
0.0
345
350
360
362
365
367
370
375
HOMO-2
HOMO
HOMO
C2-A1-C2-A1
C2-A4-C2-A4
C2-A4-C2-A1
C2-A1-C2-A4
380
300
350
400
450
500 400
500
600
700
800
 / nm
 / nm
Figure 5. a) A sketch for the co-crystallization process; b) Fluorescence
micrographs of C2-A1/A4 microcrystals prepared via co-crystallization; c)
Excitation and emission spectra of C2-A1/A4 microcrystals with a variety of
A1:A4 ratios; d) A sketch for the epitaxial growth; e) Fluorescence micrographs
of core-shell microcrystals prepared via epitaxial growth of C2-A1/A4; g)
Excitation and emission spectra of the C2-A1/A4 core-shell microcrystals.
Figure 4. Packing diagram viewed along a-axis in the single crystal
(fluorescence micrographs shown inset) structures of the isostructural double
salts C2-A1 (a), C2-A4 (b) and the triple salt C2-A1/A4 (A1:A4 = 1:1) (c); and
(d) normalized emission spectra of the respective single crystals recorded with
a fluorimeter coupled to a microscope; (e) TD-DFT calculated energy levels of
the frontier orbitals for the tetranuclear segments of C2-A1, C2-A4, and C2-
A1/A4 (with two possible sequences).
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10.1002/anie.201803965
Angewandte Chemie International Edition
COMMUNICATION
The emission color of the triple salt C2-A1/A4 could be further
tuned by adjusting the componential ratio of A1:A4 upon co-
crystallization or by epitaxial crystal growth into core-shell
microcrystals.[20]
H. Y. Zhang, J. C. Shen, C. M. Che, Synth. Met.1998, 94, 245.
[2] T. N. Singh-Rachford, F. N. Castellano, Coord. Chem. Rev.
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[3]
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O. S. Wenger, Chem. Rev. 2013, 113, 3686.
a) H. B. Wu, L. Ying, W. Yang, Y. Cao, Chem. Soc. Rev. 2009,
(1) Co-crystallization: To a methanolic solution of the cationic
C2 precursor were injected methanolic solutions of mixed
[Au(CN)2] and [AuI2] with a variety of molar ratios (Figures 5a).
The precipitates contained microcrystals in a plank-like shape
with dimensions less than 30 microns (Figures 5b). Two distinct
emission bands at peak maxima of 470 and 670 nm were
recorded with these co-crystallized microcrystals, which well-
matched the emissions from C2-A1 and C2-A1/A4 single crystals
(Figure 4), respectively. A decrease of the A1:A4 molar ratio from
199:1 to 188:12 led to an enhancement of the 670 nm band
(Figure 5c). At a certain ratio (C2:A1:A4 = 200:198:2), white light-
emitting microcrystals with CIE coordinates (0.37, 0.31) and a
quantum yield of 73% were obtained. Excitation spectra
monitored at the emission maxima of 470 and 670 nm (Figure 5c)
are identical, which implies that the two emission bands could be
ascribed to the same excited state and the lower-energy emission
is probably due to the energy-transfer from the higher energy
excitation.
38, 3391; b) G. M. Farinola, R. Ragni, Chem. Soc. Rev. 2011, 40, 3467;
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(2) Epitaxial growth: To a sample of pre-prepared microcrystals
of C2-A1 suspended in acetonitrile was added an acetonitrile
solution of [AuI2] (A4) (Figures 5d). The precipitates was
observed under a fluorescence microscope to be plank-like core-
shell microcrystals in which the blue-emissive crystals are
surrounded by an orange-emissive layer with clear boundaries
(Figures 5e). Two distinct emission bands at peak maxima of 470
and 570 nm were recorded with these core-shell microcrystals
(Figure 5f), which well-matched the emissions from C2-A1 and
C2-A4 single crystals (Figure 4), respectively. Excitation spectra
monitored at the emission maxima of 470 and 570 nm are
different (Figure 5f), which implies that the two emission bands
could be ascribed to different emissive excited states not
energetically coupled in the core-shell microcrystals.
In summary, by constructing a combinatorial pool of the
[Au(NHC)2][ML2] double salts containing infinite metallophilic
interactions in the polymeric backbones, we have achieved
tunable multi-color phosphorescence by ligand modification and
by triple-component co-crystallization or by epitaxial growth. This
work highlights that metallophilic interactions provide an entry to
new classes of organometallic phosphorescent materials with
high emission quantum yields and convenient yet versatile color
tunabilty.
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Acknowledgements
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This work was supported by the Natural Science Foundation of
China (21371175 and 21571096), the Strategic Priority Research
Program of the Chinese Academy of Sciences (XDB17000000),
and the Science and Technology Innovation Commission of
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Shenzhen
Municipality
(JCYJ20160301114634613
and
JCYJ20170817104715174).
Keywords: gold • N-heterocyclic carbenes • metallophilicity •
phosphorescence • white light-emitting
References:
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This article is protected by copyright. All rights reserved.

10.1002/anie.201803965
Angewandte Chemie International Edition
COMMUNICATION
Entry for the Table of Contents
COMMUNICATION
Cooking with colors: Correct recipes
for white light-emitting phosphors with
quantum yields higher than 70% have
been achieved in a combinatorial pool
comprised of four types of
Q. Liu, M. Xie, X. Y. Chang, S. Cao, C.
Zou, W. F. Fu, C. M. Che, Y. Chen,* and
W. Lu*
Page No. – Page No.
[Au(NHC)2]+ cations and fourteen
types of [MX2] anions, by co-
Tunable Multicolor Phosphorescence
of Crystalline Polymeric Complex
Salts with Metallophilic Backbones
crystallization or by epitaxial growth.
This article is protected by copyright. All rights reserved.