Synthesis, structures and photophysical properties of Cu(I) phosphine complexes with various diimine ligands

Article abstract of DOI:10.1016/j.poly.2017.01.046

A series of triphenylphosphine Cu(I) complexes with various diimine ligands, [Cu(N–N)(PPh₃)₂](ClO₄) [N–N = dmp (2); Ph₂Phen (3); Ph₂dmp (4); dpq (5); dppz (6); phenCN (7); phenOH (8)] are synthesized by the ligand substitution reactions of [Cu(MeCN)₄](ClO₄) with 2 mole equiv. of PPh₃ ligand and 1.2 mole equiv. of diimine ligand. {Cu(dpq)[P(XPh)₃]₂}(ClO₄) [X = Me (5a); OMe (5b); Cl (5c)] and {Cu(phenOH)[P(XPh)₃]₂}(ClO₄) [X = Me (8a); OMe (8b)] are also obtained by using various substituted phosphine ligands. These mixed-ligand complexes have been characterized using ¹H and ³¹P NMR spectroscopy, IR spectroscopy, mass spectrometry and elemental analysis. Three of these complexes have been structurally characterized by X-ray crystallography. The photophysical and electrochemical properties of these complexes have been studied. These complexes exhibit MLCT phosphorescence with emission energy, lifetimes and quantum yields showing strong dependence on the nature of diimine and phosphine ligands. In particular, both the electronic and steric effects of the substituting groups in phosphine ligands are also found to affect the emission properties of the complexes. Our study provides structural-properties information for the future design of luminescent Cu(I) complexes.

Full text of DOI:10.1016/j.poly.2017.01.046

Accepted Manuscript
Synthesis, Structures and Photophysical Properties of Cu(I) Phosphine Com-
plexes with Various Diimine Ligands
Lin-Li Hu, Chang Shen, Wing-Kin Chu, Jing Xiang, Fei Yu, Ge Xiang, Yan
Nie, Chun-Leung Kwok, Chi-Fai Leung, Chi-Chiu Ko
PII:
S0277-5387(17)30083-9
DOI:
http://dx.doi.org/10.1016/j.poly.2017.01.046
POLY 12450
Reference:
Polyhedron
To appear in:
Received Date:
Revised Date:
Accepted Date:
9 December 2016
24 January 2017
25 January 2017
Please cite this article as: L-L. Hu, C. Shen, W-K. Chu, J. Xiang, F. Yu, G. Xiang, Y. Nie, C-L. Kwok, C-F. Leung,
C-C. Ko, Synthesis, Structures and Photophysical Properties of Cu(I) Phosphine Complexes with Various Diimine
Ligands, Polyhedron (2017), doi: http://dx.doi.org/10.1016/j.poly.2017.01.046
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Synthesis, Structures and Photophysical Properties of Cu(I)
Phosphine Complexes with Various Diimine Ligands
Lin-Li Hu,[a],† Chang Shen, [a],† Wing-Kin Chu, [b,c] Jing Xiang, [a],* Fei Yu, [a] Ge Xiang, [a] Yan Nie,
[a] Chun-Leung Kwok, [d] Chi-Fai Leung, [d],* Chi-Chiu Ko*,[c]
[a] College of Chemistry and Environmental Engineering, Yangtze University, Jingzhou 434020,
HuBei, P.R. China. Email: xiangjing@yangtzeu.edu.cn
[b] Faculty of Science and Technology, Technological and Higher Education Institute of Hong
Kong, 20A Tsing Yi Road, Tsing Yi, Hong Kong, China
[c] Department of Biology and Chemistry, Institute of Molecular Functional Materials, City
University of Hong Kong, Tat Chee Avenue, Kowloon Tong, Hong Kong, China. Email:
vinccko@cityu.edu.hk
[d] Department of Science and Environmental Studies, The Education University of Hong Kong,
10 Lo Ping Road, Tai Po, Hong Kong, China. Email: cfleung@eduhk.hk
† These two authors contribute equally.
Abstract: A series of triphenylphosphine Cu(I) complexes with various diimine ligands,
[Cu(N-N)(PPh3)2](ClO4) [N-N = dmp (2); Ph2Phen (3); Ph2dmp (4); dpq (5); dppz (6); phenCN
(7); phenOH (8)] are synthesized by the ligand substitution reactions of [Cu(MeCN)4](ClO4) with
2 mole equiv. of PPh3 ligand and 1.2 mole equiv. of diimine ligand. {Cu(dpq)[P(XPh)3]2}(ClO4)
[X = Me (5a); OMe (5b); Cl (5c)] and {Cu(phenOH)[P(XPh)3]2}(ClO4) [X = Me (8a); OMe (8b)]
are also obtained by using various substituted phosphine ligands. These mixed-ligand complexes
have been characterized using 1H and 31P NMR spectroscopy, IR spectroscopy, mass spectrometry
and elemental analysis. Three of these complexes have been structurally characterized by X-ray
crystallography. The photophysical and electrochemical properties of these complexes have been
studied. These complexes exhibit MLCT phosphorescence with emission energy, lifetimes and
quantum yields showing strong dependence on the nature of diimine and phosphine ligands. In
particular, both the electronic and steric effects of the substituting groups in phosphine ligands are
also found to affect the emission properties of the complexes. Our study provides
structural-properties information for the future design of luminescent Cu(I) complexes.
Keywords: Luminescent properties; Cu(I) complexes; Crystal structures; Electrochemistry
Introduction
Phosphorescent complexes of noble metals, especially of iridium(III) and platinum(II)
complexes, have been investigated extensively due to their extensive uses as emissive dopants in
organic light-emitting diodes (OLEDs).[1] These phosphorescent materials are superior to
fluorescent materials because they can harvest both singlet and triplet excitons in
electroluminescence processes, leading to the high internal quantum efficiency.[2] These metals are,
however, very expensive, since their earth abundance are rather limited.
~ 1 ~

To develop easily accessible and sustainable luminescent materials for OLEDs, luminescent
Cu(I) complexes have received increasing attention in recent years due to their high relative
abundance, low cost, and environmentally friendly feature.[3] To improve the luminescent
properties of Cu(I) bis(diimine) [Cu(N-N)2]+ complex system, mixed-ligand Cu(I) complexes with
triphenylphosphine (PPh3) and various diimine ligands have been developed; these complexes are
demonstrated to be promising alternatives for OLEDs due to their excellent emissive properties.[3]
Until now, a number of mixed-ligand Cu(I) diimine phosphine complexes such as
[Cu(N-N)(P-P)]+ system (P-P = various bis(phosphine) ligands) have been reported and their
emission properties have been investigated in various solvents and different temperatures.[4] Some
of these complexes, particularly those with bulky PPh3 and diimine ligands, are found to be
excellent emitters as their charge-transfer (CT) excited states are not quenched by solvent-induced
exciplex.[3,4] Also, the sterically demanding ligands can impede geometric relaxation from
tetrahedral to square planar in the excited state.[5] Though the spin-orbit coupling (SOC) effect of
Cu(I) ion is weak, compared with that for iridium metal (ζCu = 857 cm-1 vs. ζIr = 3909 cm-1),[6] the
singlet state can be thermally activated at the expense of the triplet state due to the small energy
gaps ∆E(S1-T1) between the lowest singlet state and lowest triplet state in some emissive Cu(I)
complexes, leading to efficient thermally activated delayed fluorescence (TADF) at ambient
temperature.[7] With the capability to harvest both the singlet and triplet excitons, Cu(I) complexes
with TADF behavior have been considered as promising emissive dopants in electroluminescent
devices over the past few years.[8]
To further enhance the excited-state and emission properties of Cu(I) complexes, much
attention has been paid to design various diimine ligands with sterically hindered substituents in
various heteroleptic Cu(I) systems to impede the Jahn-Teller distortion in the excited state.[9]
However, related works on altering the substituents of the PPh3 are much less reported.[10] Herein,
we report the synthesis, structures of a series of Cu(I) complexes with various diimine and
phosphine ligands. In addition, their photophysical and electrochemical properties have also been
investigated in detail.
Results and discussion
Synthesis and Characterizations
The precursor complex [Cu(MeCN)4](ClO4) was prepared according to the literature
procedure.[11] Through the ligand substitution reaction of the precursor with 2 mole equiv. of PPh3
ligand afforded initially the complex [Cu(MeCN)2(PPh3)2]+ (1)[12] and it then reacted with 1.2
mole equiv. of different diimine ligands in acetonitrile solution at ambient temperature to give the
Cu(I) triphenylphosphine complexes with various diimine ligands, [Cu(N-N)(PPh3)2](ClO4) [N-N
= dmp (2); Ph2Phen (3); Ph2dmp (4); dpq (5); dppz (6); phenCN (7); phenOH (8)] (Scheme 1).
Using a similar synthetic strategy except that the substituted phosphine ligands are used instead of
PPh3, {Cu(dpq)[P(XPh)3]2}(ClO4) [X = Me (5a); OMe (5b); Cl (5c)] and
{Cu(phenOH)[P(XPh)3]2}(ClO4) [X = Me (8a); OMe (8b)] are obtained. After slow evaporation
of the solutions of these complexes, analytically pure complexes were isolated as yellow or orange
microcrystalline solids. All these mixed-ligand complexes have been characterized using 1H and
31P NMR spectroscopy, IR spectroscopy, mass spectrometry and elemental analysis. The structures
of 2, 5c, and 7 have also been confirmed by X-ray crystallography.
~ 2 ~

Scheme 1. Synthetic route for [Cu(MeCN)2(PPh3)2]+ (1) and {Cu(NN)[P(XPh)3]2}+ (28).
X-ray Crystal Structure Determination
By slow evaporation of solutions of the complexes, single crystals of 2, 5c and 7, with quality
suitable for X-ray crystal structure determination were obtained. Perspective drawings of the
cations of these complexes are shown in Figure 1. The selected bond lengths (Å) and angles (º),
and the structure determination data are summarized in Table 1 and Table S1, respectively. As
shown in the structures of 2, 5c and 7, all these complexes display distorted tetrahedral geometry
(Figure 1). The bite angles of diimine ligands are in the range of 79.4(5)−80.5(2)°, which are
smaller than 90°. This is due to the steric requirement of chelating ligands and is commonly
observed in related diimine transition metal complexes.[13] In addition, these Cu(I) complexes
show PCuP bond angles ranging from 123.57(7)−124.21(8)°, which are similar to those in the
related bis(phosphine) Cu(I) complexes.[14] Comparing the dihedral angles between PCuP and
NCuN planes of these complexes [(2): 96.7(1)°; (5c) 90.7°; (7) 81.7°], a smaller dihedral angle
is observed in 7, which is probably due to the steric effect of asymmetric phenCN ligand in 7. The
CuN and CuP bond distances are in the typical range of 2.068(6)2.128(13) Å and
2.211(2)2.284(4) Å respectively, which are comparable with those in the related Cu(I)
complexes.[14] Except for 7, 2 and 5c show similar CuN bond distances. The deviation of the
CuN bond distance (CuN1: 2.104(5) Å, CuN2: 2.082(5) Å) in 7 is attributed to the
asymmetrical chemical environment and electron-withdrawing cyano group of phenCN ligand.
~ 3 ~

Figure 1. The cationic structures of (a) 2, (b) 5c and (c) 7. Hydrogen atoms are omitted for clarity.
Table 1. Selected bond parameters (Å, °) for 1, 2, 5c, and 7.
2
5c
7
CuN1 (Å)
2.126(13)
2.128(13)
2.282(4)
2.284(4)
79.4(5)
123.6(16)
2.078(6)
2.068(6)
2.274(2)
2.211(2)
80.5(2)
124.21(8)
2.104(5)
2.082(5)
2.264(2)
2.267(2)
79.7(2)
123.57(7)
CuN2 (Å)
CuP1 (Å)
CuP2 (Å)
N1CuN2 (°)
P1CuP2 (°)
In addition to the above bonding environments, intramolecular π-stacking interactions are
also observed for 2 and 5c. In the structure of 2 (Figure S1), a phenyl ring of P(ClPh)3 ligand
exhibits intramolecular π-stacking with the central phenyl ring of dpq ligand with
centroid-to-centroid distance of 3.65(1) Å, while the intramolecular π-stacking interaction arises
between the phenyl rings of two different PPh3 ligands for 2. In contrast to 2 and 5c, similar
intramolecular π-stacking interaction is not observed in 7, while extensive intermolecular
π-stacking between the adjacent phenCN ligands, with the centroid-to-centroid distance of 4.05(2)
Å, is found (Figure S2).
UV-vis Absorption Properties
The UV-vis absorption properties of these complexes have been investigated in CH2Cl2 solution.
The overlaid absorption spectra are shown in Figure 2 and the absorption data are summarized in
Table 2. All of these complexes (except 1) show intense ligand-centered (LC) π→π* absorptions
of phosphine and diimine ligands with molar extinction coefficients on the order of 104 dm3 mol-1
cm-1 in the UV region (220290 nm). As with other Cu(I) diimine diphosphino complexes,[15]
these complexes also show 1MLCT [d(Cu)→π*(NN)] transition at the lower energy region
(340–410 nm). This assignment is supported by the dependence of the absorption energy on the
electronic nature of the diimine ligands, which is in line with the energy level of π* orbital of the
diimine ligands for complexes containing the same phosphine ligands.[16] In addition, the lowest
energy absorptions of these complexes are sensitive to the nature of phosphine ligands. The
increase of the π-accepting ability of the phosphine ligands [P(C6H4OMe)3 < P(tol)3 < PPh3 <
P(C6H4Cl)3] results also in the blue-shift of the low-energy absorption for the complexes with the
same diimine ligand [5b (407 nm) > 5a (391 nm) > 5 (384 nm) > 5c (377 nm)]. The increasing
MLCT absorption energy of the complexes is probably due to the better stabilization of d(Cu)
~ 4 ~

orbital, as reflected by the anodically shifted metal-centered oxidation potentials (see below) in the
presence of stronger π-accepting phosphine ligands.
Figure 2. Overlaid UV/vis absorption spectra of (a) 2–4, (b) 5–8 and (c) 5, 5a–5c in CH2Cl2
solution.
Table 2. Uv/vis absorption data of 1–8 in CH2Cl2 solution at 298 K.
Absorption λabs / nm (ε / dm3 mol−1 cm−1
)
1
2
3
4
5
227 (39290), 258(20900)
229 (73040), 274(44710), 373sh (1300)
228 (71180), 285 (58210), 381sh (5810)
228 (68830), 287 (53890), 369sh (3950)
226 (38620), 257 (48370), 384sh (2890)
5a
5b
5c
6
228 (50950), 258 (56390), 391sh (2600)
227 (57060), 254 (79870), 407sh (2800)
227 (75600), 258 (70700), 377sh (1620)
227 (38180), 277 (56690), 365 (10060)
227 (46090), 278 (30780), 403 (2090)
228 (64230), 258sh (37950), 370sh (3070)
229 (84440), 264 (40660), 369sh (3800)
231(78300), 266 (62200), 369sh (2950)
7
8
8a
8b
Emission Properties
~ 5 ~

Upon photo-excitation (λex = 420 nm), these phosphine-containing Cu(I) diimine complexes
(28) in CH2Cl2 solution at room temperature show yellow to red MLCT [d(Cu)→π*(NN)]
phosphorescence with a structureless emission band peaking at 542667 nm. The emission
lifetimes are in the range of 0.02 to 27.6 μs. The emission data of the complexes are listed in Table
3 and the overlaid emission spectra of selected complexes are shown in Figure 3. Similar to the
trend observed in the MLCT absorption energy of these complexes, their emission energy shows a
trend consistent with the π-accepting ability of the diimine ligands [8 (611 nm) > 3 (626 nm) > 5
(629 nm) > 7 (667 nm)] (Figure 3a).[16] Among these complexes, 2 (λem = 551 nm) and 4 (λem
=
542 nm) show the substantially higher emission energy in CH2Cl2 solution. This is ascribed to the
steric effect of two methyl groups on the 2,9-positions of phen, which preclude the structural
distortion on the excited state.[17] The large geometry change of CT excited state due to the lack of
sterically hindering substituents on the 2,9-positions of diimine ligands for other complexes is
suggested by the large Stokes shift observed in their emission spectra. For 7 and 8, which contain
only one substituent on the α-position of the diimine ligands, the emission also exhibit larger
Stokes shift as in those complexes with unsubstituted diimine ligands. The results reveal that the
mono-substituted diimine ligand actually has negligible effect on precluding the structural
distortion on the excited state.
By comparing the MLCT phosphorescence of complexes bearing varied phosphine ligands [5,
5a–5c (Figure 3b) and 8, 8a–8b], but the same dimine ligand, it is noted that the emission energy
not only varies with the electronic effect of the phosphine ligands but also with their steric
properties. The introduction of both electron-donating and electron-withdrawing substituents in
the phosphine ligands leads to a blue-shifted emission. This should be rationalized by following
factors: (i) The electron-withdrawing Cl group on the phosphine ligands could lead to the
blue-shifted emission, as it could can stabilize the d(Cu) orbital and other occupied orbitals; (ii) It
is well known that the structural rearrangement of Cu(I) complexes in their excited states typically
leads to a red shift in emission which reduces the energy gap. The substitution of protons on the
phosphine ligands by Cl or Me/MeO groups will result in the enhancement of the bulkiness in
phosphine ligands and further inhibit the structural distortion in the excited state. Although the
Me/MeO groups on the phoshphine ligand will increase the energy level of HOMO, they could
effectively inhibit the structural distortion in the excited state and thus result in higher energy
emission. This factor will also results in the blue-shift of the luminescence.[18] From the above
variation trends, the steric effect is more pronounced than the electronic effect on the phosphine
ligands. The more pronounced blue-shift is observed for 5c as the electron-withdrawing Cl
substituents have dual effects on its emission.
In solid state, these complexes show intense green to orange-red (519 to 629 nm)
photoluminescence (Table 3, Figure 4). The intense solid emissions of these complexes are
attributed to the decrease in the excited state distortion of Cu(I) complexes and non-radiative
decay in solid state. Since the rigidochromic effect impedes the structural distortion in the excited
state, the solid-state emissions for most of these Cu(I) complexes are blue-shifted relative to their
solution emissions.[19] In contrast to the solution emissions of these complexes, their solid
emission show different variation trend on the electronic properties of phosphine ligands and
diimine ligands. The deviation of the trend in their solid emission can be explained by the various
factors such as inter- and inner-molecular π-stacking in these solid state, as similar to the previous
solid emissions of related Cu(I) complexes.[20,21] In 77 K EtOH-MeOH (4:1, v/v) glassy medium,
~ 6 ~

these complexes display intense luminescence (Figure 5 and Table 3). Except for 6, these
complexes show structureless emission bands. Compared with their solution emission, the
emissions are generally blue-shifted and longer-lived. This is also attributed to the rigidochromic
effect commonly observed in MLCT emitters.[20,21] The submicrosecond excited state lifetimes in
the glassy medium at 77 K further support the assignment of triplet excited state origin. These
emissions are also tentatively assigned to be derived from 3MLCT [d(Cu)→π*(N^N)]
excited-state origin. The emission band of 6 in low-temperature glassy medium is highly
structured with vibrational progression spacing of ~1200 cm-1.[22] The significant different
emission characteristics of 6 is suggestive of a different emission origin at low temperature, which
is ascribed to the 3LC excited state origin of the dppz ligand.
Figure 3. (a) Overlaid emission spectra of 2, 4, 5, 7 and 8 in CH2Cl2 at room temperature; (b)
Overlaid emission spectra of 5, 5a–5c in CH2Cl2 at room temperature.
~ 7 ~

Figure 4. (a) Overlaid solid state emission spectra of 3, 4, 5 and 6 at room temperature; (b)
Overlaid solid state emission spectra of 5, 5a–5c at room temperature.
Figure 5. Overlaid emission spectra of 2, 4, 5 and 7 (a) and 5, 5a-5c (b) in glassy medium at 77 K.
Table 3. The emission data for compounds 3–8.
Medium
Emission
ema / nm (τo/ µs)

em (× 103) c
(T / K)
(3)
CH2Cl2 (298)
Glass c (77)
Soild
626 (0.2)
0.2
146
0.5
535(160.2)
536 (1.8)
(4)
CH2Cl2 (298)
Glass c (77)
Soild
542 (27.6)
530 (282.5)
519 (10.1)
629 (0.1)
(5)
CH2Cl2 (298)
Glass c (77)
Soild
569 (103.2)
587 (0.2)
(5a)
(5b)
(5c)
(6)
CH2Cl2 (298)
Glass c (77)
Soild
613 (0.02)
569 (145.5)
537 (8.5)
0.7
CH2Cl2 (298)
Glass c (77)
Soild
602 (0.02)
575 (158.5)
582 (0.9)
0.7
0.5
0.5
1.0
6.4
CH2Cl2 (298)
Glass c (77)
Soild
587 (0.03)
582 (80.1)
541 (7.5)
CH2Cl2 (298)
Glass c (77)
Soild
620 (0.02)
546, 590, 635 (0.29)
629 (0.12)
667 (0.37)
577 (203.2)
588 (4.4)
(7)
CH2Cl2 (298)
Glass c (77)
Soild
(8)
CH2Cl2 (298)
Glass c (77)
Soild
611 (1.3)
549 (146.1)
541 (5.9)
(8a)
CH2Cl2 (298)
605 (0.69)
5.6
~ 8 ~

Glass c (77)
Soild
551 (195.2)
554 (5.6)
(8b)
CH2Cl2 (298)
Glass c (77)
Soild
603 (0.23)
567 (213.4)
544 (11.4)
2.9
Electrochemistry
The redox properties of the Cu(I) complexes in acetonitrile containing 0.1 M nBuNPF6 were
recorded by cyclic voltammetry (CV) and the corresponding electrochemical data were
summarized in Table 4. Representative CVs of these complexes are shown in Figure 6. Complex 1
shows an irreversible metal-centered oxidation potential at Epa = 0.31 V (vs Cp2Fe+/0). Except for 2
and 4, all the complexes showed an irreversible oxidation wave with Epa in the range of +0.85 to
+1.05 V vs Cp2Fe+/0, which are comparable with those commonly observed in the Cu(I) diimine
complex systems. They are assigned to metal-centered CuII/I oxidation. Such an assignment is
supported by the dependence of the potential on the substituents and π-conjugating effects of the
diimine ligand, similar to those reported in the related complexes.[3,4] In general, a higher
oxidation potential is observed for complex bearing phosphine and diimine ligands of stronger
π-accepting properties, which better stabilize the d(Cu) orbital. The influence of the substituents
on the phosphine ligands towards the metal-centered oxidation is more significant than that of the
diimine ligands. An investigation of complexes with the same diimine ligand but different
phosphine ligands shows that the positions of oxidation couples are in line with the π-accepting
ability of the phosphine ligands, which is in the order 5c (+1.05 V) > 5 (+0.87 V) > 5a (+0.73 V) >
5b (+0.49 V).
In the reduction scan, except for 8, 8a and 8b, these complexes all show a reversible reduction
couple at approx. 2 V vs. Cp2Fe+/0. The high sensitivity of the reduction potential to the
electronic nature of diimine ligand is suggestive of the ligand-centered reduction.[16]
Table 4. Electrochemical data with 0.1 M [nBu4N]PF6 in MeCN at 298 K.a
Oxidation Epa
(vs. Fc+/0) [V]b
0.31
Reduction E1/2 or
Epa (vs. Fc+/0) [V]b (∆Ep [mV])c
1
/
2
3
4
5
5a
5b
5c
6
7
8
0.63
0.85
0.61
0.87
0.73
0.49
1.05
0.88
-2.07(64)
-1.92(71)
-2.00(69)
-1.84(60)
-1.85(68)
-1.86(72)
-1.82(94)
-1.45(64)
-1.57(56)
-1.86
0.85
0.89
8a
8b
0.78
0.77
-2.09
-2.07
a Working electrode: glassy carbon; scan rate, 100 mV s-1. b E1/2 is (Epa + Epc)/2 and ∆Ep = |Epa -
Epc|, where Epa and Epc are the anodic and cathodic peak potentials respectively.c
~ 9 ~

Figure 6. Cyclic voltammograms of (a) 2 and (b) 5c in 0.1 M [nBu4N]PF6 MeCN solution with
scan rate = 100 mVs-1.
Conclusions
We have studied a new series of luminescent Cu(I) diimine phosphino complexes. These
complexes exhibit MLCT phosphorescence with emission energy, lifetimes and quantum yields
strongly dependence on the nature of the diimine and phosphine ligands. It is worth to note that
both the electronic and steric effects of substituting groups in phosphine ligands affect
significantly the emission properties of these complexes. Our work should provide
structural-properties information for the future design of luminescent Cu(I) complexes.
Experimental
Materials and reagents
2,9-Dimethyl-1,10-phenanthroline (dmp), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline
(Ph2dmp) and 4,7-diphenyl-1,10-phenanthroline (Ph2phen) were purchased from Acros Organic
Chemical Company. Triphenylphosphine (PPh3), tri(p-tolyl)phosphine [P(MePh)3],
tri(4-methoxyphenyl)phosphine [P(MeOPh)3] and tri(4-chlorophenyl)phosphine [P(ClPh)3] were
purchased from Strem Chemical Company. These commercially available reagents were used
without further purification. 2-Hydroxyl-1,10-phenanthroline (phenOH),[23]
2-cyano-1,10-phenanthroline (phenCN),[24] dipyrido[3,2-d:2',3'-f]quinoxaline (dpq),[25]
dipyridophenazine (dppz),[11] and the complexes [Cu(MeCN)4](ClO4) (1)[12] and
[Cu(PPh3)2(dmp)](ClO4) (2) [26] were synthesized according to literature procedures. All other
reagents and solvents were of analytical grade and were used without further purification.
Synthesis
All reactions were carried out under strictly anaerobic conditions under an inert argon
atmosphere by using standard Schlenk techniques.
~ 10 ~

[CuI(PPh3)2(Ph2Phen)](ClO4) (3) [CuI(MeCN)4](ClO4) (50 mg, 0.15 mmol), PPh3 (80.4 mg, 0.30
mmol) and Ph2Phen (55.9 mg, 0.17 mmol) in MeCN (15 ml) are stirred at room temperature for 1
h. Slow evaporation of a MeCN solution of 3 afforded analytically pure complex as yellow
crystalline solid. Yield (93.1 mg, 59.8 %). Elemental analysis for C60H46ClCuN2O4P2: calcd. C
70.65, H 4.55, N 2.75%; found: C 70.60, H 4.70, N 2.77%. Selected IR (KBr, cm-1): v(Cl-O) 1111.
ESI-MS (positive): m/z 919 (M+). 1H NMR (300 MHz, CDCl3): δ 8.83 (d, J = 5.0 Hz, 2H, phen H);
8.01 (s, 2H, phen H); 7.74 (d, J = 5.0 Hz, 2H, phen H); 7.62 (m, 6H, phenyl H); 7.57–7.51 (m, 4H,
phenyl H); 7.37 (m, 6H, phenyl H); 7.26–7.14 (m, 24H, phenyl H). 31P{1H} NMR (162 MHz,
CDCl3): δ 2.97 (s, PPh3). UV/Vis (CH3CN): λmax /nm (ε /mol–1 dm3 cm–1): 228 (71180), 285
(58210), 381 sh (5810).
[CuI(PPh3)2(Ph2dmp)](ClO4) (4) [CuI(MeCN)4](ClO4) (50mg, 0.15 mmol), PPh3 (80.4 mg, 0.30
mmol) and Ph2dmp (60.7 mg, 0.18 mmol) in MeCN (15 ml) are stirred at room temperature for 1
h. Slow evaporation of a MeCN solution of 4 afforded analytically pure complex as yellow
crystalline solid. Yield (93.4 mg, 62.9 %). Elemental analysis for C62H50ClCuN2O4P2: calcd. C
71.06, H 4.81, N 2.67%; found: C 71.12, H 4.90, N 2.62%. Selected IR (KBr, cm-1): v(Cl-O) 1110.
ESI-MS (positive): m/z 947 (M+). 1H NMR (300 MHz, CDCl3): δ 7.98 (s, 2H, Phen H); 7.60 (m,
6H, phenyl H); 7.57–7.53 (m, 4H, phenyl H); 7.44 (s, 2H, phen H); 7.38–7.42 (m, 6H, phenyl H);
7.26–7.21 (m, 24H, phenyl H); 2.31 (s, 6H, -CH3). 31P{1H} NMR (162 MHz, CDCl3): δ 0.87 (s,
PPh3). UV/Vis (CH3CN): λmax /nm (ε /mol–1 dm3 cm–1): 228 (68830), 287 (53890), 369 sh (3950).
[CuI(PPh3)2(dpq)](ClO4) (5) [CuI(MeCN)4](ClO4) (50 mg, 0.15 mmol), PPh3 (80.4 mg, 0.30
mmol) and dpq (39.0 mg, 0.18 mmol) in MeCN (15 ml) are stirred at room temperature for 1 h.
Recrystallization by slow diffusion of diethyl ether into a CH2Cl2 solution of 5 afforded
analytically pure complex as yellow crystalline solid. Yield (88.4 mg, 62.9 %). Elemental analysis
for C50H38ClCuN4O4P2: calcd. C 65.29, H 4.16, N 6.09%; found: C 65.27, H 4.22, N 6.04%.
Selected IR (KBr, cm-1): v(Cl-O) 1093. ESI-MS (positive): m/z 819 (M+). 1H NMR (300 MHz,
CDCl3): δ 9.63 (d, J = 8.1 Hz, 2H, dpq H); 8.90 (s, 2H, dpq H); 8.03 (d, J = 7.7 Hz, 2H, dpq H);
7.31–7.36 (m, 6H, phenyl H); 7.13–7.23 (m, 24H, phenyl H). 31P{1H} NMR (162 MHz, CDCl3): δ
2.50 (s, PPh3). UV/Vis (CH3CN): λmax /nm (ε /mol–1 dm3 cm–1): 226 (40320), 257 (48370), 384 sh
(2890).
[CuI{P(PhMe)3}2(dpq)](ClO4) (5a) [CuI(MeCN)4](ClO4) (50 mg, 0.15 mmol), P(PhMe)3 (93.1
mg, 0.30 mmol) and dpq (39.0 mg, 0.18 mmol) in MeCN (15 ml) are stirred at room temperature
for 1 h. Recrystallization by slow diffusion of diethyl ether into a CH2Cl2 solution of 5a afforded
analytically pure complex as yellow crystalline solid. Yield (80.2 mg, 52.3 %). Elemental analysis
for C56H50ClCuN4O4P2: calcd. C 66.99, H 5.02, N 5.58%; found: C 66.80, H 5.13, N 5.60%.
Selected IR (KBr, cm-1): v(Cl-O) 1094. ESI-MS (positive): m/z 903 (M+). 1H NMR (300 MHz,
CDCl3): δ 9.61 (d, J = 7.3 Hz, 2H, dpq H); 9.15 (s, 2H, dpq H); 8.87 (s, 2H, dqp H); 8.01 (dd, J =
8.1, 4.9 Hz, 2H, dpq H); 7.13–6.89 (m, 24H, phenyl H); 2.28 (s, 18H, -CH3). 31P{1H} NMR (162
MHz, CDCl3): δ 2.39 (s, PPh3). UV/Vis (CH3CN): λmax /nm (ε /mol–1 dm3 cm–1): 228 (73590), 258
(56390), 391 sh (2600).
[CuI{P(PhOMe)3}2(dpq)](ClO4) (5b) [CuI(MeCN)4](ClO4) (50 mg, 0.15 mmol), P(MeOPh)3
(107.8 mg, 0.30 mmol) and dpq (39.0 mg, 0.18 mmol) in MeCN (15 ml) are stirred at room
temperature for 1 h. Recrystallization by slow diffusion of diethyl ether into a CH2Cl2 solution of
5b afforded analytically pure complex as yellow crystalline solid. Yield (82.3 mg, 48.9 %).
Elemental analysis for C56H50ClCuN4O10P2: calcd. C 61.15, H 4.58, N 5.09%; found: C 61.05, H
~ 11 ~

4.62, N 5.01%. Selected IR (KBr, cm-1): v(Cl-O) 1097. ESI-MS (positive): m/z 999 (M+). 1H NMR
(300 MHz, CDCl3): δ 9.59 (dd, J = 8.2, 1.3 Hz, 2H, dpq H); 9.13 (s, 2H,dpq H); 8.97 (d, J = 4.3
Hz, 2H, dpq H); 8.05 (dd, J = 8.2, 4.8 Hz, 2H, dpq H); 7.07 (d, J = 8.2 Hz, 12H, phenyl H); 6.71
(d, J = 8.7 Hz, 12H, phenyl H); 3.76 (s, 18H, -OMe H). 31P{1H} NMR (162 MHz, CDCl3): δ 0.36
(s, PPh3). UV/Vis (CH3CN): λmax /nm (ε /mol–1 dm3 cm–1): 227 (57060), 254 (79870), 407 sh
(2800).
[CuI{P(PhCl)3}2(dpq)](ClO4) (5c) [CuI(MeCN)4](ClO4) (50 mg, 0.15 mmol), P(PhCl)3 (111.1 mg,
0.30 mmol) and dpq (39.0 mg, 0.18 mmol) in MeCN (15 ml) are stirred at room temperature for 1
h. Slow evaporation of a MeCN solution of 5c afforded analytically pure complex as yellow
crystalline solid. Yield (90.7 mg, 52.8 %). Elemental analysis for C50H32Cl7CuN4O4P2: calcd. C
53.31, H 2.81, N 4.97%; found: C 53.35, H 2.95, N 4.89%. Selected IR (KBr, cm-1): v(Cl-O) 1110.
ESI-MS (positive): m/z 1023 (M+). 1H NMR (300 MHz, CDCl3): δ 9.64 (d, J = 8.1 Hz, 2H, dqp H);
9.16 (s, 2H, dpq H); 9.10 (d, J = 4.0 Hz, 2H, dpq H); 8.13 (dd, J = 8.2, 4.7 Hz, 2H, dpq H);
7.24–7.26 (m, 12H, phenyl H); 7.07–7.12 (m, 12H, phenyl H). 31P{1H} NMR (162 MHz, CDCl3):
δ 0.36 (s, PPh3). UV/Vis (CH3CN): λmax /nm (ε /mol–1 dm3 cm–1): 227 (75600), 258 (70700), 377
sh (1620).
[CuI(PPh3)2(dppz)](ClO4) (6) [CuI(MeCN)4](ClO4) (50 mg, 0.15 mmol), PPh3 (80.4 mg, 0.30
mmol) and dppz (47.5 mg, 0.18 mmol) in MeCN (15 ml) are stirred at room temperature for 1 h.
Slow evaporation of a MeCN solution of 6 afforded analytically pure complex as yellow
crystalline solid. Yield (80.3 mg, 50.6 %). Elemental analysis for C54H40ClCuN4O4P2: calcd. C
66.87, H 4.16, N 5.78%; found: C 66.80, H 4.20, N 5.75%. Selected IR (KBr, cm-1): v(Cl-O) 1094.
ESI-MS (positive): m/z 792 (M+). 1H NMR (300 MHz, CDCl3): δ 9.76 (dd, J = 8.2, 1.5 Hz, 2H,
dppz H); 8.88 (dd, J = 4.9, 1.5 Hz, 2H, dppz H) ; 8.45 (dd, J = 6.6, 3.4 Hz, 2H, dppz H); 8.11–7.98
(m, 4H, dppz H); 7.39–7.30 (m, 6H, phenyl H); 7.25–7.08 (m, 24H, phenyl H). 31P{1H} NMR
(162 MHz, CDCl3): δ 3.58 (s, PPh3). UV/Vis (CH3CN): λmax /nm (ε /mol–1 dm3 cm–1): 227 (38180),
277 (56694), 362 (10190).
[CuI(PPh3)2(PhenCN)](ClO4) (7) [CuI(MeCN)4](ClO4) (50 mg, 0.15 mmol), PPh3 (80.4 mg, 0.30
mmol) and phenCN (34.5 mg, 0.18 mmol) in MeCN (15 ml) are stirred at room temperature for 1
h. Recrystallization by slow diffusion of diethyl ether into a CH2Cl2 solution of 7 afforded
analytically pure complex as yellow crystalline solid. Yield (89.4 mg, 65.6 %). Elemental analysis
for C49H37ClCuN3O4P2: calcd. C 65.92, H 4.18, N 4.71%; found: C 65.99, H 4.20, N 4.78%.
Selected IR (KBr, cm-1): v(C≡N) 1969; v(Cl-O) 1111. ESI-MS (positive): m/z 792 (M+). 1H NMR
(300 MHz, CDCl3): δ 8.90 (d, J = 8.3 Hz, 1H, phenCN H); 8.74–8.66 (m, 1H, phenCN H); 8.31 (q,
J = 9.0 Hz, 2H, phenCN H); 8.22 (s, 1H, phenCN H); 8.00 (d, J = 8.3 Hz, 1H, phenCN H); 7.76
(dd, J = 8.0, 4.7 Hz, 1H, phenCN H); 7.42–7.32 (m, 6H, phenyl H); 7.24–7.05 (m, 24H, phenyl H).
31P {1H} NMR (162 MHz, CDCl3): δ 3.56 (s, PPh3). UV/Vis (CH3CN): λmax /nm (ε /mol–1 dm3
cm–1): 227 (46090), 278 (30780), 403 (2090).
[CuI(PPh3)2(phenOH)](ClO4) (8) [CuI(MeCN)4](ClO4) (50 mg, 0.15 mmol), PPh3 (80.4 mg, 0.30
mmol) and phenOH (33.2 mg, 0.18 mmol) in MeCN (15 ml) are stirred at room temperature for 1
h. Slow evaporation of a MeCN solution of 8 afforded analytically pure complex as yellow
crystalline solid. Yield (79.4 mg, 58.8 %). Elemental analysis for C48H38ClCuN2O5P2: calcd. C
65.23, H 4.33, N 3.17%; found: C 65.20, H 4.42, N 3.20%. Selected IR (KBr, cm-1): v(Cl-O) 1094.
ESI-MS (positive): m/z 867 (M+). 1H NMR (300 MHz, CDCl3): δ 10.70 (s, 1H, -OH H); 8.33 (d, J
= 8.2 Hz, 1H, phen H); 8.28 (d, J = 3.5 Hz, 1H, phen H); 8.20 (d, J = 8.9 Hz, 1H, phen H); 7.86 (d,
~ 12 ~

J = 8.8 Hz, 1H, phen H); 7.72 (d, J = 8.8 Hz, 1H, phen H); 7.65 (d, J = 9.1 Hz, 1H, phen H); 7.48
(dd, J = 8.1, 4.7 Hz, 1H); 7.35–7.43 (m, 6 H, phenyl H); 7.17–7.27 (m, 24 H, phenyl H). 31P{1H}
NMR (162 MHz, CDCl3): δ 0.08 (s, PPh3). UV/Vis (CH3CN): λmax /nm (ε /mol–1 dm3 cm–1): 228
(64230), 258 sh (37950), 370 sh (3070).
[CuI{P(PhMe)3}2(phenOH)](ClO4) (8a) [CuI(MeCN)4](ClO4) (50 mg, 0.15 mmol), P(PhMe)3
(93.1 mg, 0.30 mmol) and phenOH (33.2 mg, 0.18 mmol) in MeCN (15 ml) are stirred at room
temperature for 1 h. Slow evaporation of a MeCN solution of 8a afforded analytically pure
complex as yellow crystalline solid. Yield (73.5 mg, 49.7 %). Elemental analysis for
C54H50ClCuN2O5P2: calcd. C 67.01, H 5.21, N 2.89%; found: C 67.10, H 5.23, N 2.94%. Selected
IR (KBr, cm-1): v(Cl-O) 1094. ESI-MS (positive): m/z 867 (M+). 1H NMR (300 MHz, CDCl3): δ
10.61 (s, 1H,-OH H); 8.31 (s, 1H, phen H) ; 8.29 (d, J = 2.0 Hz, 1H, phen H); 8.18 (d, J = 8.8 Hz,
1H, phen H); 7.82 (d, J = 8.8 Hz, 1H, phen H); 7.67 (dd, J = 12.5, 9.4 Hz, 1H, phen H); 7.55 (dd, J
= 11.8, 8.1 Hz, 1H, phen H); 7.47 (dd, J = 7.4, 5.4 Hz, 1H, phen H); 7.02–7.08 (m, 12 H, phenyl
H); 6.91–6.95 (m, 12 H, phenyl H); 2.30 (s, 18H, -CH3). 31P{1H}NMR (162 MHz, CDCl3): δ 0.36
(s, PPh3). UV/Vis (CH3CN): λmax /nm (ε /mol–1 dm3 cm–1): 229 (84440), 264 (40660), 369 sh
(3800).
[CuI{P(PhOMe)3}2(phenOH)](ClO4) (8b) [CuI(MeCN)4](ClO4) (50 mg, 0.15 mmol), P(PhOMe)3
(107.8 mg, 0.30 mmol) and phenOH (33.2 mg, 0.18 mmol) in MeCN (15 ml) are stirred at room
temperature for 1 h. Slow evaporation of a MeCN solution of 8b afforded analytically pure
complex as yellow crystalline solid. Yield (76.2 mg, 46.9%). Elemental analysis for
C54H50ClCuN2O11P2: calcd. C 60.96, H 4.74, N 2.63%; found: C 60.75, H 4.79, N 2.56%. Selected
IR (KBr, cm-1): v(Cl-O) 1097. ESI-MS (positive): m/z 963 (M+). 1H NMR (300 MHz, CDCl3):
δ10.59 (s, 1H, -OH H); 8.41–8.35 (m, 1H, phen H) ; 8.32 (dd, J = 8.2, 1.3 Hz, 1H, phen H); 8.18
(d, J = 8.5 Hz, 1H, phen H); 7.83 (d, J = 8.8 Hz, 1H, phen H); 7.71 (d, J = 8.8 Hz, 1H, phen H);
7.59 (dd, J = 13.0, 4.3 Hz, 1H, phen H); 7.51 (dd, J = 8.1, 4.7 Hz, 1H, phen H); 7.09 (d, J = 7.7 Hz,
12H, phenyl H); 6.67 (d, J = 8.6 Hz, 12H, phenyl H); 3.78 (s, 18H, -CH3). 31P{1H} NMR (162
MHz, CDCl3): δ 0.87 (s, PPh3). UV/Vis (CH3CN): λmax /nm (ε /mol–1 dm3 cm–1): 231(78300), 266
(62200), 369 sh (2950).
Physical measurements and instrumentation
1H NMR and 31P{1H} NMR spectra were recorded on a Bruker AV300 (300 MHz) FT-NMR
spectrometer. Chemical shifts (δ, ppm) are reported relative to tetramethylsilane (Me4Si). All
positive-ion ESI mass spectra were recorded on a PE-SCIEX API 150 EX single-quadruple mass
spectrometer. Elemental analysis was performed on an Elementar Vario MICRO Cube elemental
analyzer. IR spectra of the solid samples as KBr discs were obtained within the range 4000–400
cm-1 on an AVATAR 360 FTIR spectrometer. All of the electronic absorption spectra were
recorded on a Hewlett–Packard 8453 or Hewlett–Packard 8452A diode-array spectrophotometer.
Steady-state emission spectra were measured at RT and at 77 K on a Horiba JobinYvon
Fluorolog-3-TCSPC spectrofluorometer. The solutions were rigorously degassed on a
high-vacuum line in a two-compartment cell with not less than four successive freeze–pump–thaw
cycles. The measurements at 77 K were carried out on dilute solutions of the samples in
EtOH/MeOH (4:1 v/v) loaded in a quartz tube inside a quartz-walled Dewar flask that contained
liquid nitrogen. Luminescence quantum yields were determined using the optical dilution method
described by Demas and Crosby[27] with an aqueous solution of [Ru(bpy)3]Cl2 (ϕem = 0.042[28]
~ 13 ~

with 436 nm excitation) at room temperature as reference. Luminescence lifetimes were measured
by using the time-correlated single-photon-counting (TCSPC) technique on a Fluorolog-3-TCSPC
spectrofluorometer in a fast MCS mode with a Nano LED-375 LH excitation source, which had a
peak excitation wavelength at 375 nm and a pulse width of less than 750 ps. The photon-counting
data were analyzed on Horiba Jobin Yvon Decay Analysis Software.
Cyclic Voltammetry (CV)
Measurements were performed on a CH Instruments, Inc. Model CHI 620 Electrochemical
Analyzer. Electrochemical measurements were performed in MeCN solution with [nBu4N]PF6
(0.1M) as a supporting electrolyte at room temperature. The reference electrode was Ag/AgCl
(0.1M in MeCN) electrode and the working electrode was a glassy carbon electrode (CH
Instruments, Inc.) with platinum wire as the counter electrode. The surface of the working
electrode was polished with a 1 μm a-alumina slurry (Linde) and then with a 0.3 μm a-alumina
slurry (Linde) on a microcloth (Buehler Co.). The ferrocenium/ferrocene+/0 couple (FeCp2+/0) was
used as an internal reference. All of the solutions for the electrochemical studies were de-aerated
with pre-purified argon gas prior to the measurements.
X-ray Crystal Structure Determination
The crystal structures were determined on an Oxford Diffraction Gemini S Ultra X-ray
single-crystal diffractometer by using graphite-monochromated Cu-Ka radiation (λ = 1.5417 Å).
The structures were solved by using direct methods with the SHELXS-97 program.[29] The Ru
atoms and many of the non-hydrogen atoms were located according to the direct methods. The
positions of the other non-hydrogen atoms were located after refinement by full-matrix
least-squares by using the SHELXL-97 program.[30] In the final stage of the least-squares
refinement, all non-hydrogen atoms were refined anisotropically. H atoms were generated by
using the SHELXL-97 program. The positions of H atoms were calculated based on the riding
model with thermal parameters that were 1.2 times that of the associated C atoms and participated
in the calculation of the final R indices. CCDC-1498290 (2), 1498291 (5c), and 1498292 (7)
contain the supplementary crystallographic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
Acknowledgements
The authors gratefully acknowledge the financial support of the Natural Science Foundation of
China (21201023) and the Science and Technology Project of Jingzhou Technology Division
(2016AD50-5). Financial support from the Hong Kong Research Grant Council (28300014 and
18300715) and The Education University of Kong Kong (04024-ECR-16) are also gratefully
acknowledged.
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A series of luminescent Cu(I) complexes bearing various diimine and phosphine ligands have been
obtained and their luminescent properties are significantly influenced by the nature of diimine
and PPh3 ligands.
~ 18 ~