Article

pubs.acs.org/IC

Luminescent Three- and Four-Coordinate Dinuclear Copper(I)

Complexes Triply Bridged by Bis(diphenylphosphino)methane and
Functionalized 3‑(2′-Pyridyl)-1,2,4-triazole Ligands
Li-Hua He,† Yan-Sheng Luo,† Bao-Sheng Di,† Jing-Lin Chen,*,†,‡ Cheuk-Lam Ho,*,§ He-Rui Wen,†
Sui-Jun Liu,† Jin-Yun Wang,*,∥ and Wai-Yeung Wong*,‡,§
†
School of Science and School of Metallurgy and Chemical Engineering, Jiangxi University of Science and Technology, Ganzhou
341000, People’s Republic of China
‡
Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom, Hong Kong,
People’s Republic of China
§
Institute of Molecular Functional Materials and Department of Chemistry, Hong Kong Baptist University, Waterloo Road, Kowloon
Tong, Hong Kong, People’s Republic of China
∥
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences,
Fuzhou 350002, People’s Republic of China
*
S Supporting Information

ABSTRACT: A new series of bimetallic Cu(I) complexes 1−5 triply bridged by a

monoanionic or charge-neutral functionalized 3-(2′-pyridyl)-1,2,4-triazole in a
μ−η1(N),η2(N,N) tridentate binding mode and two bis(diphenylphosphino)methane
(dppm) ligands have been synthesized. Complexes 1−5 are singly or doubly charged
dinuclear Cu(I) species with an eight-membered Cu2C2P4 ring of {Cu(μ-dppm)2Cu}
unit, in which 3 and 4 adopt the boat−boat conformation, while 1, 2, and 5 display the
chair−boat form. In these dimeric copper(I) complex cations, one of the two Cu(I)
ions is four-coordinated, in a highly distorted N2P2 tetrahedral environment and the
other is three-coordinated, in a distorted NP2 trigonal planar arrangement. All these
Cu(I) complexes exhibit a comparatively weak low-energy absorption in CH2Cl2
solution, ascribed to the charge-transfer transitions with appreciable 1MLCT
contribution, as suggested by time-dependent density functional theory (TDDFT)
analyses. Complexes 1−5 display good emission properties in both solution and solid states at ambient temperature, which are
well-modulated via structural modification of 3-(2′-pyridyl)-1,2,4-triazole, including the alteration of the substituent type (−CF3,
−H, −CH3, and −C(CH3)3) and position (ortho-, meta-, and para-position). Furthermore, the variation of the substituent (−CF3
and −C(CH3)3) on the 5-site of the 1,2,4-triazolyl ring markedly influences the proton activity of the 1,2,4-triazolyl-NH, thus
leading to the formation of both singly and doubly charged bimetallic Cu(I) species regulated by the NH ↔ N− conversion,
resulting from NH deprotonation of the 1,2,4-triazolyl ring.

■ INTRODUCTION
There has been considerable research interest in luminescent
metal complexes, because of their promising potential in
materials science.1 Continuing efforts have been devoted to the
development of metal-based phosphors with emission colors in
the entire visible region2 and the most representative examples
are d6- and d8-metal complexes of the third-row transition metal
series such as Os, Ir, and Pt.3 However, because of the high cost
and limited availability of these precious metals, more attention
has been paid to develop inexpensive alternatives in the past
two decades.4 Recently, copper(I) system has become a class of
important emissive metal complexes, because of their promising
application perspectives in optoelectronic devices and the high
relative abundance and environmental friendliness of cop-
per.5−7 In this aspect, heteroleptic Cu(I) complexes have been
most extensively investigated, particularly copper(I)-diimine-
phosphine complexes,8 and some organic light-emitting devices
(OLEDs) doped with such emitters have also been fabricated.9
It is well-known that the electronic property, steric bulk, and
rigidity of the diimine ligand all play a significant role in
determining the luminescence properties of Cu(I) complexes,
and structural modification of common diimine ligands, such as
2,2′-bipyridine and 1,10-phenanthroline, and the use of
previously unemployed ligands are two effective approaches.
Moreover, the rational choice of auxiliary diphosphine ligands is
also useful for improving the emission properties of Cu(I)
complexes. For instance, those Cu(I) diimine complexes with
bis[2-(diphenylphosphino)phenyl]ether (DPEphos) generally
show markedly improved luminescence properties and stability
Received: May 11, 2017
Published: August 21, 2017

© 2017 American Chemical Society 10311 DOI: 10.1021/acs.inorgchem.7b01159

Inorg. Chem. 2017, 56, 10311−10324
Inorganic Chemistry
in their OLEDs.10 Furthermore, it is also notable that the
diphosphine-bridged bimetallic Cu(I) complex
[Cu2(dmp)2(dppb)2](PF6)2 shows a higher quantum yield
and a longer emission lifetime than the chelating mononuclear
Cu(I) species [Cu(dmp)(dppe)](PF6) and [Cu(dmp)(dppp)]-
(PF6), where dmp = 2,9-dimethyl-1,10-phenanthroline, dppe =
1,2-bis(diphenylphosphino)ethane, dppp = 1,3-bis-
(diphenylphosphino)propane, and dppb = 1,4-bis-
(diphenylphosphino)butane.8c This suggests that constructing
dinuclear Cu(I) system with bridging diphosphine instead of
chelating diphosphine, such as the Cu(I) system with the
[Cu2(μ-dppm)2]2+ motif, may be another alternative possibility
for improving emission properties.
Compared to mononuclear and multinuclear Cu(I) systems,
photoactive bimetallic Cu(I) species have been less studied,
especially those bearing the Cu2(μ-dppm)2 core. Among the
Cu2(μ-dppm)2-based system,11 the two Cu(I) centers all being
four-coordinate are the most common and the two Cu(I) ions
all being three-coordinate can also be often seen,11c−l whereas
three- and four-coordinate dinuclear Cu(I) complexes have
been scarcely reported,11b,m−q only including a polydentate
diimine-based dicopper(I) complex.11b As a continuation of our
work in the 1,2,4-triazole-based Cu(I) coordination chem-
istry,12 it is expected that polydentate 3-(2′-pyridyl)-1,2,4-
triazole ligand can be incorporated into the [Cu2(μ-dppm)2]2+
component to develop new emissive molecular materials based
on dinuclear Cu(I) complexes. More interestingly, in this study,
it is found that the functionalized 3-(2′-pyridyl)-1,2,4-triazole
ligand can coordinate with the [Cu2(μ-dppm)2]2+ unit using an
unexpected μ−η1(N),η2(N,N) tridentate coordination mode
instead of a common η2(N,N) bidentate chelating manner.
Moreover, to the best of our knowledge, this type of three- and
four-coordinate dinuclear copper(I) complexes triply bridged
by functionalized 3-(2′-pyridyl)-1,2,4-triazole and diphosphine
mixed ligands have not been reported hitherto. We describe
herein the synthesis, characterization, and luminescence
properties of a new series of three- and four-coordinate
bimetallic copper(I) complexes triply bridged by two dppm
ligands and a monoanionic or charge-neutral functionalized 3-
(2′-pyridyl)-1,2,4-triazole ligand in a μ−η1(N),η2(N,N) triden-
tate binding mode.
■
EXPERIMENTAL SECTION
General Procedures and Materials. All reactions were
performed under a N2 atmosphere using anhydrous solvents or
solvents treated with an appropriate drying reagent. Commercially
available reagents were used without further purification, unless
otherwise stated. Different functionalized 3-(2′-pyridyl)-1,2,4-triazole
ligands including 5-trifluoromethyl-3-(6′-methyl-2′-pyridyl)-1H-1,2,4-
triazole (o-fmptzH), 5-trifluoromethyl-3-(5′-methyl-2′-pyridyl)-1H-
1,2,4-triazole (m-fmptzH), 5-trifluoromethyl-3-(4′-methyl-2′-pyridyl)-
1H-1,2,4-triazole (p-fmptzH), 5-trifluoromethyl-3-(2′-pyridyl)-1H-
1,2,4-triazole (fptzH), and 5-tert-butyl-3-(6′-methyl-2′-pyridyl)-1H-
1,2,4-triazole (o-bmptzH) were synthesized using previously reported
procedures.13 Chart 1 shows the structures of these ligands.
Caution! Perchlorate salts are potentially explosive and should be
handled caref ully in small amount.
Preparation of [Cu2(μ-dppm)2(μ−η1(N),η2(N,N)-o-fmptz)](ClO4)
(1). An admixture of [Cu(CH3CN)4](ClO4) (33.2 mg, 0.101 mmol)
and o-fmptzH (11.5 mg, 0.050 mmol) in CH2Cl2 (5 mL) was stirred
for 30 min at room temperature; dppm (39.2 mg, 0.102 mmol) was
then added and the mixture was stirred for another 2 h to get a light
yellow solution. The solvent was evaporated to dryness under reduced
pressure. The residue was then dissolved in CH2ClCH2Cl/CH2Cl2 (v/
v, 1:5), and slow diffusion of petroleum ether into the above mixture
10312
Article
Chart 1
gave light yellow crystals of 1 (44.2 mg, 0.036 mmol, 72%). 1H NMR
(CD2Cl2, 400 MHz): δ 8.12 (d, 1H, J = 8 Hz), 7.83 (t, 1H, J = 6 Hz),
7.45 (s, 2H), 7.38 (d, 2H, J = 4 Hz), 7.30−7.13 (m, 26H), 7.02 (d, 3H,
J = 8 Hz), 6.80 (s, 4H), 6.55 (s, 4H), 3.41 (s, 2H), 3.16 (s, 2H), 1.87
(s, 3H). 31P NMR (CD2Cl2, 202.3 MHz): δ −9.55 (s, 2P, dppm),
−10.92 (s, 2P, dppm). Anal. Calcd for C59H50ClCu2F3N4O4P4: C,
57.97; H, 4.12; N, 4.58. Found: C, 57.93; H, 4.15; N, 4.62. Selected IR
(KBr, cm−1): 1096 vs (ClO4−).
Preparation of [Cu2(μ-dppm)2(μ−η1(N),η2(N,N)-m-fmptz)](ClO4)
(2). Complex 2 was similarly prepared according to the procedure for
1 by using [Cu(CH3CN)4](ClO4), m-fmptzH, and dppm. Light yellow
crystals were obtained by slow diffusion of n-hexane into a
CH3COCH3/CH2Cl2 (v/v, 1:5) mixture of 2 (yield: 70%). 1H
NMR (CD2Cl2, 400 MHz): δ 8.16 (d, 1H, J = 8 Hz), 7.87 (s, 1H),
7.71 (d, 1H, J = 8 Hz), 7.35 (d, 8H, J = 4 Hz), 7.26−7.18 (m, 18H),
7.07 (t, 4H, J = 8 Hz), 7.00 (t, 2H, J = 6 Hz), 6.78 (t, 4H, J = 8 Hz),
6.59 (s, 4H), 3.32 (s, 4H), 2.16 (s, 3H). 31P NMR (CD2Cl2, 202.3
MHz): δ −11.05 (s, 4P, dppm). Anal. Calcd for
C59H50ClCu2F3N4O4P4: C, 57.97; H, 4.12; N, 4.58. Found: C,
57.92; H, 4.14; N, 4.63. Selected IR (KBr, cm−1): 1095 vs (ClO4−).
Preparation of [Cu2(μ-dppm)2(μ−η1(N),η2(N,N)-p-fmptz)](ClO4)
(3). Complex 3 was similarly prepared according to the procedure
for 1 by using [Cu(CH3CN)4](ClO4), p-fmptzH, and dppm. Light
yellow crystals were obtained by slow diffusion of n-hexane into a
CH2ClCH2Cl/CH2Cl2 (v/v, 1:5) mixture of 3 (yield: 72%). 1H NMR
(CD2Cl2, 400 MHz): δ 8.15 (s, 1H), 8.13−8.08 (m, 1H), 7.34−7.07
(m, 27H), 7.01−6.94 (m, 6H), 6.73 (t, 4H, J = 8 Hz), 6.53 (s, 4H),
3.29 (s, 4H), 2.47 (s, 3H). 31P NMR (CD2Cl2, 202.3 MHz): δ −12.82
(s, 4P, dppm). Anal. Calcd for C59H50ClCu2F3N4O4P4: C, 57.97; H,
4.12; N, 4.58. Found: C, 58.01; H, 4.15; N, 4.55. Selected IR (KBr,
cm−1): 1096 vs (ClO4−).
Preparation of [Cu2(μ-dppm)2(μ−η1(N),η2(N,N)-fptz)](ClO4) (4).
Complex 4 was similarly prepared according to the procedure for 1 by
using [Cu(CH3CN)4](ClO4), fptzH, and dppm. Colorless crystals
were isolated by the slow diffusion of petroleum ether into a
CH3COCH3/CH2Cl2 (v/v, 1:5) mixture of 4 (yield: 75%). 1H NMR
(CD2Cl2, 400 MHz): δ 8.31 (d, 1H, J = 4 Hz), 8.24−8.19 (m, 1H),
7.96 (t, 1H, J = 6 Hz), 7.31−6.99 (m, 34H), 6.76 (s, 4H), 6.57 (s, 4H),
3.36 (s, 4H). 31P NMR (CD2Cl2, 202.3 MHz): δ −11.35 (s, 4P,
dppm). Anal. Calcd for C58H48ClCu2F3N4O4P4: C, 57.65; H, 4.00; N,
4.64. Found: C, 57.68; H, 4.03; N, 4.62. Selected IR (KBr, cm−1):
1095 vs (ClO4−).
Preparation of [Cu2(μ-dppm)2 (μ−η1(N),η2(N,N)-o-bmptzH)]-
(ClO4)2 (5). Complex 5 was similarly prepared according to the
procedure for 1 by using [Cu(CH3CN)4](ClO4), o-bmptzH, and
dppm. Colorless crystals were obtained by slow diffusion of petroleum
ether into a CH3OH/CHCl3 (v/v, 1:5) mixture of 5 (yield: 83%).
Anal. Calcd for C62H60Cl2Cu2N4O8P4: C, 56.80; H, 4.61; N, 4.27.
Found: C, 56.84; H, 4.58; N, 4.25. Selected IR (KBr, cm−1): 1098 vs
(ClO4−).
Crystal Structural Determination. Crystal data of 1−5 were
collected on a Bruker D8 QUEST diffractometer with graphite-
monochromated Mo Kα radiation (λ = 0.71073 Å). The program
SAINT was used for integration of the diffraction profiles. Structures
were solved by direct methods and refined by full-matrix least-squares
technique on F2 using the SHELXTL software package.14 Scheme 1
shows depictions of these structures. The heavy atoms were located
DOI: 10.1021/acs.inorgchem.7b01159
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Inorganic Chemistry
Scheme 1. Structures of Bimetallic Cu(I) Complexes 1−5
from E-map and other non-hydrogen atoms were found in subsequent
difference Fourier syntheses. All non-hydrogen atoms were refined
anisotropically, while hydrogen atoms were generated geometrically
with isotropic thermal parameters.
Physical Measurements. 1H and 31P NMR spectra were recorded
on Bruker Avance III (400 MHz) NMR spectrometer with SiMe4 as
the internal reference. Infrared (IR) spectra were collected on a Bruker
Optics ALPHA FT-IR spectrometer using KBr pellets. Elemental
analyses (C, H and N) were conducted on a PerkinElmer Model 240C
elemental analyzer, where all the crystal samples were used after
grinding and drying under vacuum. Ultraviolet-visible light (UV-vis)
absorption spectra in CH2Cl2 solution were measured on a Shimadzu
Model UV-2550 spectrometer. The photoluminescence properties in
CH2Cl2 solution and in the solid state were determined on a
fluorescence spectrometer (Edinburgh, Model F900) with a thermo-
electrically cooled photomultiplier tube (Hamamatsu, Model R3809).
The luminescence quantum yields (Φem) in CH2Cl2 solution at
ambient temperature were calculated by Φs = Φr(Br/Bs)(nr/ns)2(Ds/
Dr), using fluorescein in H2O as the standard (Φem = 0.79), where the
subscripts “r” and “s” denote the reference standard and the sample
solution, respectively, and n, D, and Φ are the refractive index of the
solvents, the integrated intensity, and the luminescence quantum yield,
respectively.15 The quantity B is calculated by B = 1−10−AL, where A is
the absorbance at the excitation wavelength and L is the optical path
length. An integrating sphere (Lab sphere) was applied to measure the
luminescence quantum yield in the solid state. The cyclic voltammo-
grams were obtained with a potential/galvanostat analyzer (Princeton
Applied Research, Model 263A), using a standard three-electrode
setup consisting of a glassy carbon disk working electrode, a platinum
counter electrode, and a Ag/AgCl reference electrode. All the
experiments were carried out in dry and nitrogen-saturated CH2Cl2
solutions with 0.1 M n-tertrabutylammonium hexafluorophosphate as
the supporting electrolyte. The potentials are quoted versus the
ferrocenium/ferrocene couple (Fc+/0 = 0.51 V).
Computational Methodology. All the calculations were carried
out by using the Gaussian 09 program package16 to gain an insight into
the photophysical properties of the 3-(2′-pyridyl)-1,2,4-triazole-based
bimetallic Cu(I) complexes 1, 4, and 5. First, the density functional
theory (DFT)17 method at the restricted and unrestricted gradient
corrected correlation functional PBE1PBE18 levels, respectively, was
used to optimize the ground state (S0) and the lowest-energy triplet
excited state (T1) geometries of complexes 1, 4, and 5 without
symmetry constraint. The initial structures were extracted from the
crystallographically determined geometries. During the optimization
processes, the convergent values of maximum force, root-mean-square
(RMS) force, maximum displacement, and RMS displacement were
set by default. To analyze the spectroscopic properties, 80 singlet
excited states and 6 triplet excited states for 1, 4, and 5 in CH2Cl2
solution were calculated by the time-dependent density functional
theory (TDDFT)19 method at the same functional used in the
geometrical optimization, respectively, based on the optimized ground-
10313
Article
state S0 and lowest-energy triplet excited-state T1 geometries. The
solvent effects in CH2Cl2 media were taken into account by
performing the self-consistent reaction field (SCRF) calculations,
using the polarizable continuum model method (PCM).20 In these
calculations, the Stuttgart−Dresden basis set21 consisting of the
effective core potentials (ECP) was employed for the Cu and P atoms,
and 6-31G(p,d) basis set22 for the remaining atoms were used.
Visualization of the frontier molecular orbitals was performed by
GaussView. The Ros and Schuit method (C-squared population
analysis method, SCPA)23 is supported to analyze the partition orbital
composition by using Multiwfn 3.3.8 program.24
■
RESULTS AND DISCUSSION
Syntheses and Characterizations. Dinuclear Cu(I)
complexes 1−5 were prepared by treating [Cu(CH3CN)4]-
(ClO4) with the corresponding functionalized 3-(2′-pyridyl)-
1,2,4-triazole (o-fmptzH, m-fmptzH, p-fmptzH, fptzH, and o-
bmptzH) and dppm in a 2:1:2 molar ratio. Complexes 1−4 are
readily soluble in CH2Cl2, CHCl3, and CH2ClCH2Cl, whereas
complex 5 shows poor solubility in common organic solvents
including DMSO and DMF. In the 1H NMR spectra of 1−4 in
CD2Cl2, besides the aromatic proton signals (δ 8.31−6.53
ppm) and the C−H resonances of the methylene (δ 3.41−3.16
ppm) and methyl (δ 2.47−1.87 ppm) groups, the characteristic
N−H proton signal of the 1,2,4-triazolyl ring was not observed,
indicating that functionalized 3-(2′-pyridyl)-1,2,4-triazole ligand
with a trifluoromethyl group easily undergoes the 1,2,4-
triazolyl-NH deprotonation and coordinates to the Cu(I) ion
as a monoanionic ligand, as supported by X-ray crystallography
(vide infra). The methylene protons of two dppm (PCH2P)
ligands display two unresolved broad singlet peaks at 3.41 and
3.16 ppm for 1, while only one unresolved broad singlet peak is
detected at 3.32, 3.29, and 3.36 ppm for 2, 3, and 4,
respectively,11c−h which are closely related to the (ABXX′)2 or
(ABX2)2 spin system of the two sets of chemically inequivalent
protons (CHaHbPP′ or CHaHbP2) in the Cu2(μ-dppm)2-based
complexes.11c,d Similarly, the 31P NMR spectra exhibit two
unresolved broad peaks at −9.55 and −10.92 ppm for 1 and
only one unresolved broad singlet peak at −11.05, −12.82, and
−11.35 ppm for 2, 3, and 4, respectively,11c−h which are
associated with the variation of the difference of the two
chemically inequivalent P atoms (CuPCHaHbP′Cu′) in the
Cu2(μ-dppm)2-based complexes,11c,d as supported by the larger
difference of the Cu1−N1 and Cu2−N3 bond lengths of 1
(0.221 Å) caused by the ortho-methyl group, with respect to
those of 2−4 (0.076−0.120 Å). On the other hand, these
DOI: 10.1021/acs.inorgchem.7b01159
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Inorganic Chemistry Article

Table 1. Crystal Data and Structure Refinement for Compounds 1−5

compound 1 2 3 4 5
formula C61H54Cl5Cu2F3N4O4P4 C61H54Cl5Cu2F3N4O4P4 C59H54ClCu2F3N4O6P4 C58H50ClCu2F3N4O5P4 C62H62Cl2Cu2N4O9P4
formula weight, fw 1392.29 1392.29 1258.47 1226.43 1329.02
temperature, T (K) 301(2) 293(2) 293(2) 293(2) 296(2)
crystal system orthorhombic orthorhombic monoclinic triclinic monoclinic
space group P212121 P212121 P21/c P 1̅ P21/n
a (Å) 13.4601(12) 13.3562(10) 17.7631(9) 11.5041(5) 19.4953(8)
b (Å) 21.4200(19) 21.4838(16) 15.7497(8) 14.1636(6) 13.9432(7)
c (Å) 22.3367(19) 22.4402(16) 23.4965(12) 18.2652(8) 23.1516(10)
α (deg) 90 90 90 86.5740(10) 90
β (deg) 90 90 107.1730(10) 85.9450(10) 92.812(2)
γ (deg) 90 90 90 72.5520(10) 90
V (Å3) 6440.0(10) 6439.0(8) 6280.4(6) 2829.8(2) 6285.6(5)
Z 4 4 4 2 4
ρcalcd (g cm−3) 1.436 1.436 1.331 1.439 1.404
μ (mm−1) 1.024 1.024 0.880 0.973 0.921
no. reflections collected 127615 92766 126052 37634 42969
no. unique reflections 14167 11435 14981 12874 11660
Rint 0.0626 0.0537 0.0371 0.0295 0.0606
no. observed reflections 14167 11435 14981 12874 11660
no. parameters 748 750 758 721 757
GOF on F2 1.096 1.049 1.086 1.018 1.125
R1 [I > 2σ(I)] 0.0650 0.0521 0.0795 0.0464 0.1082
wR2 0.1423 0.1244 0.2365 0.1126 0.2926

Table 2. Selected Bond Lengths and Angles of Compounds 1−5

compound 1 2 3 4 5
Bond Lengths (Å)
Cu1−N1 2.236(7) 2.168(5) 2.159(4) 2.157(2) 2.220(3)
Cu1−N2 2.044(6) 2.043(4) 2.017(4) 2.033(2) 2.060(3)
Cu1−P1 2.255(2) 2.2637(14) 2.2488(12) 2.2474(8) 2.2666(11)
Cu1−P3 2.278(2) 2.2374(15) 2.2470(12) 2.2361(8) 2.2728(12)
Cu2−N3 2.025(6) 2.048(5) 2.047(4) 2.081(2) 2.046(3)
Cu2−P2 2.222(2) 2.2416(14) 2.2427(12) 2.2439(8) 2.2078(12)
Cu2−P4 2.241(2) 2.2271(15) 2.2447(12) 2.2545(8) 2.2401(12)
Cu1···Cu2 3.1363(11) 3.0852(8) 3.1099(8) 3.0493(5) 3.0846(7)
Bond Angles (deg)
N1−Cu1−N2 76.4(2) 77.41(17) 77.31(16) 77.54(9) 74.97(12)
N1−Cu1−P1 116.1(2) 102.03(14) 114.69(10) 111.46(7) 118.38(9)
N1−Cu1−P3 104.00(19) 115.12(14) 113.74(10) 110.89(7) 103.90(9)
N2−Cu1−P1 115.24(19) 104.31(13) 116.18(11) 111.13(7) 112.77(9)
N2−Cu1−P3 104.09(19) 115.14(13) 116.13(11) 115.97(7) 105.20(10)
P1−Cu1−P3 128.54(7) 130.02(5) 113.89(5) 121.48(3) 128.50(4)
N3−Cu2−P2 116.75(19) 108.95(14) 113.08(11) 116.65(7) 123.33(10)
N3−Cu2−P4 108.04(19) 117.38(14) 113.20(11) 112.01(7) 106.94(10)
P2−Cu2−P4 133.23(7) 131.75(5) 130.80(5) 129.70(3) 128.79(4)

unusual signal splittings displayed in the 1H and 31P NMR
spectra of 1 at room temperature can also be clearly observed in
the variable-temperature 1H and 31P NMR spectra of the
representative complex 2 in CD2Cl2 from 298 to 198 K (see
Figures S16 and S17 in the Supporting Information),
suggesting the significant influence of the ortho-methyl
substituent on the 2-pyridyl ring. Similarly, this signal
coalescence phenomenon that the (PCH2P)2 system only
exhibits an unresolved broad singlet peak in the 1H and 31P
NMR spectra of 2−4 at room temperature can also be well-
presented in the variable-temperature 1H and 31P NMR spectra
of 1 in DMSO-d6 from 298 to 368 K (see Figures S18 and S19
in the Supporting Information). Therefore, all these data
10314
further suggest that the substituent type and position on the 2-
pyridyl ring have some impact on the coordination environ-
ment around the Cu(I) center, especially for the ortho-methyl
group.
The structures of 1−5 were established by single-crystal X-
ray diffraction. The crystallographic data and structure
refinement details of 1−5 are summarized in Table 1, and
selected bond lengths and angles are listed in Table 2.
Complexes 1−4 with a trifluoromethyl group are all singly
charged bimetallic Cu(I) species with an eight-membered
Cu2C2P4 ring of {Cu(μ-dppm)2Cu} unit, showing the chair−
boat conformation for 1 and 2 and the boat−boat form for 3
and 4 (see Figures 1−4),11 in which these functionalized 5-
DOI: 10.1021/acs.inorgchem.7b01159
Inorg. Chem. 2017, 56, 10311−10324
Inorganic Chemistry Article

Figure 1. Perspective drawing of the cation of 1, showing 30%

probability thermal ellipsoids and atomic numbering scheme. Hydro-
gen atoms and phenyl rings have been omitted for the sake of clarity.

Figure 3. Perspective drawing of the cation of 3, showing 30%

probability thermal ellipsoids and atomic numbering scheme. Hydro-
gen atoms and phenyl rings have been omitted for the sake of clarity.

Figure 2. Perspective drawing of the cation of 2, showing 30%

probability thermal ellipsoids and atomic numbering scheme. Hydro-
gen atoms and phenyl rings have been omitted for the sake of clarity.

trifluoromethyl-3-(2′-pyridyl)-1,2,4-triazole ligands adopt a

monoanionic μ−η1(N3),η2(N1,N2) coordination mode as a
result of the deprotonation of the 1,2,4-triazolyl-NH,25
chelating the Cu1 atom via its two N donors (N1 and N2)
and binding to the Cu2 atom via the N3 donor adjacent to the
N2 atom. Different from 1−4 with a trifluoromethyl group,
compound 5 with a tert-butyl group is a doubly charged
dinuclear Cu(I) species with an o-bmptzH ligand exhibiting a
charge-neutral μ−η1(N3),η2(N1,N2) coordination fashion Figure 4. Perspective drawing of the cation of 4, showing 30%
without the 1,2,4-triazolyl-NH deprotonation (Figure 5),26 in probability thermal ellipsoids and atomic numbering scheme. Hydro-
which the dimeric {Cu(μ-dppm)2Cu} cation features a chair− gen atoms and phenyl rings have been omitted for the sake of clarity.
boat conformation of eight-membered Cu2C2P4 ring. In these
dimeric cationic units, the two Cu(I) metal centers doubly
bridged by a pair of dppm ligands are further bridged by one two new bimetallic seven-membered Cu2P2N2C rings with
functionalized 3-(2′-pyridyl)-1,2,4-triazole ligand to generate diverse Cu···Cu separations ranging from 3.0493 Å to 3.1363
10315 DOI: 10.1021/acs.inorgchem.7b01159
Inorg. Chem. 2017, 56, 10311−10324
Inorganic Chemistry
Figure 5. Perspective drawing of the cation of 5, showing 30%
probability thermal ellipsoids and atomic numbering scheme. Hydro-
gen atoms except H4A and phenyl rings have been omitted for the
sake of clarity.
Å,11n,27 which are longer than the sum of the van der Waals
radii of two Cu ions (2.80 Å)28 and thus too long to qualify as a
metal−metal bond. The two Cu atoms of the cations for 1−5
possess two different coordination environments, namely,
tetrahedral and trigonal distorted arrangements, and a similar
structure has only been found in the bimetallic Cu(I) complex
[Cu2(μ-dppm)2{(S,S)-iPr-pybox}](PF6)2 ((S,S)-iPr-pybox =
2,6-bis[4′-(S)-isopropyloxazolin-2′-yl]pyridine).11b For 1−5,
the Cu1 center is located in a highly distorted P2N2 tetrahedral
environment formed by two P atoms from two different dppm
ligands and two N atoms from the 2-pyridyl and 1,2,4-triazolyl
moieties of functionalized 3-(2′-pyridyl)-1,2,4-triazole, with the
Cu1−Ntriazolyl lengths (2.044(6), 2.043(4), 2.017(4), 2.033(2),
and 2.060(3) Å for 1−5, respectively) being much shorter than
the Cu1−Npyridyl lengths (2.236(7), 2.168(5), 2.159(4),
2.157(2), and 2.220(3) Å for 1−5, respectively), suggesting a
stronger bonding of Cu(I) to the N donor of the 1,2,4-triazolyl
ring.12 The Cu2 center coordinates to the other two P atoms of
the two different dppm bridges and one N atom from the 1,2,4-
triazolyl moiety of 3-(2′-pyridyl)-1,2,4-triazole, in a distorted
P2N trigonal planar arrangement. It is noteworthy that the
Cu1−N1 and Cu1−N2 lengths of 4 are somewhat shorter,
whereas the Cu2−N3 distance is slightly longer, compared to
those of 1−3, suggesting that the introduction of the methyl
group into the 2-pyridyl ring exerts two different effects on the
Cu1 and Cu2 cores. Moreover, the Cu−Npyridyl length of 5 is
slightly shortened, whereas the Cu−Ntriazolyl distances are
somewhat elongated, relative to those of 1, and the N−H
deprotonation occurring in 1 is not observed in 5, indicating
that the substituent type on the 1,2,4-triazolyl ring has two
diverse effects on the 2-pyridyl and 1,2,4-triazolyl moieties of
the functionalized 3-(2′-pyridyl)-1,2,4-triazole and the proton
activity of the 1,2,4-triazolyl-NH. For 1−3 with methyl group at
different substituent positions, it is noted that the Cu1−N1 and
Cu1−N2 lengths are decreased gradually (1 > 2 > 3), whereas
the Cu2−N3 distance is basically unchanged, except for that of
1 due to the effect of the ortho-methyl group, implying that the
methyl position at the 2-pyridyl ring has different effects on the
10316
Article
Cu1 core and the ortho-methyl group exerts a more marked
influence on the Cu2 core, compared to the meta- and para-
methyl groups, as supported by the 1H and 31P spectra of 1
being markedly different from those of 2 and 3 at room
temperature. The P2−Cu2−P4 angle (128.79(4)°−
133.23(7)°) for 1−5 is larger than the regular trigonal value
of 120°, forcing smaller values for the N3−Cu2−P2 and N3−
Cu2−P4 angles. Analogously, the P1−Cu1−P3 angle
(121.48(3)°−130.02(5)°) for 1−2 and 4−5 is also larger
than the ideal tetrahedral value of 109°28′, whereas the
abnormal P1−Cu1−P3 angle of 113.89(5)° is observed in 3,
more close to the ideal tetrahedral value, which may result in
the anomaly of the emission properties of 3, compared to those
of 1 and 2 with methylated 5-trifluoromethyl-3-(2′-pyridyl)-
1,2,4-triazole ligand.
Photophysical and Electrochemical Properties. As
shown in Figure 6, five functionalized 3-(2′-pyridyl)-1,2,4-
Figure 6. Absorption spectra of five free ligands and their
corresponding complexes 1−5 in CH2Cl2 solution at ambient
temperature.
triazole ligands exhibit multiple absorption bands in the UV
region (<310 nm) in CH2Cl2 solution, attributed to the ligand-
centered 1[π → π*] transitions. Their absorption spectra
display certain red-shifting (p-fmptzH < fptzH < m-fmptzH < o-
fmptzH < o-bmptzH), because of the variation of the electron-
donating ability and position of the substituents on 3-(2′-
pyridyl)-1,2,4-triazole. As depicted in Figure 6 and Table 3,
these bimetallic Cu(I) complexes 1−5 display several
absorption peaks in the 230−320 nm region (ε > 104 M−1
cm−1); those are attributable to the 1[π → π*] transitions of
both functionalized 3-(2′-pyridyl)-1,2,4-triazole and dppm
ligands, which are somewhat red-shifted, because of the
more-extended π-conjugation, compared to the five free
ligands. In addition, only comparatively weak low-energy
absorption tails (ε < 5500 M−1 cm−1) are observed in the
range of 320−400 nm for 1−5, suggesting that these weak low-
energy absorptions are not markedly influenced by the
functionalization of 3-(2′-pyridyl)-1,2,4-triazole.8k,12 As sug-
gested by TDDFT calculations (vide infra), the lowest-lying
electronic transitions of 1−5 are assigned to Cu/diphosphine
→ diimine charge transfer (metal-to-ligand and ligand-to-ligand
charge transfer, 1MLCT/1LLCT) transitions, mixed with
different degrees of intraligand (1IL) charge transitions inside
functionalized 3-(2′-pyridyl)-1,2,4-triazole ligands.4,8k,11b−j,12
As depicted in Figures 7 and 8, these dinuclear Cu(I)
complexes 1−5 show broad and unstructured emission band
peaking at 502, 520, 517, 528, and 520 nm with moderate
DOI: 10.1021/acs.inorgchem.7b01159
Inorg. Chem. 2017, 56, 10311−10324
Inorganic Chemistry Article

Table 3. Photophysical and Electrochemical Data of Compounds 1−5

compound medium λabs [nm] ε [M−1 cm−1] λem [nm] τ [μs] Φem [%] Epab [V]
o-fmptzH CH2Cl2 239 22200 417
246 19930
282 18295
290 14880

m-fmptzH CH2Cl2 245 25460 433

281 16350
288 13700

p-fmptzH CH2Cl2 242 25580 422

275 16020
282 13720

fptzH CH2Cl2 238 21610 432

245 19260
276 14840
284 11440

o-bmptzH CH2Cl2 247 17610 343

285 19660
294 15360

1 CH2Cl2 270 23040 502 11.2 4.1 1.65

307 10980
solid 481 (506)a 43.1 (163)a 40.6

2 CH2Cl2 269 23900 520 9.8 17.7 1.54

306 10100
solid 493 (518)a 68.6 (322)a 46.0

3 CH2Cl2 270 24120 517 9.4 10.7 1.59

305 10080
solid 495 (515)a 38.3 (159)a 80.6

4 CH2Cl2 269 26300 528 12.0 37.7 1.58

305 10935
solid 499 (519)a 46.7 (123)a 61.8

5 CH2Cl2 271 21530 520 10.3 8.8

309 8760
solid 494 (512)a 31.1 (115)a 75.5
a b
Value shown in parentheses represents data measured in the solid state at 77 K. Anodic peak potentials were quoted versus the ferrocenium/
ferrocene reference (Fc+/0 = 0.51 V); oxidation potentials were measured in dry CH2Cl2.

quantum yields of 0.041, 0.177, 0.107, 0.377 and 0.088,
respectively, in degassed CH2Cl2 solution at ambient temper-
ature. The luminescence intensity is drastically quenched by the
presence of oxygen in aerated solution. Together with their
relatively long luminescence lifetimes, from several to a dozen
microseconds, it is suggested that the emission may be
phosphorescent in origin.10f,12 The emission of 1 (502 nm) is
blue-shifted by 18 nm, relative to that of 5 (520 nm), as a
consequence of the replacement of an electron-donating tert-
butyl group on the 1,2,4-triazolyl ring by an electron-
withdrawing trifluoromethyl group, resulting in the 1,2,4-
triazolyl-NH deprotonation of 1 and the negative charge of the
1,2,4-triazolyl ring, which raises the energy level of LUMO and,
hence, enlarges the HOMO−LUMO energy gap and gives an
emission with higher energy.8k,12 This also suggests that the
deprotonation of the 1,2,4-triazolyl-NH would give a more
10317
pronounced effect on the emission properties, relative to the
introduction of a strong electron-withdrawing trifluoromethyl
group into the 1,2,4-triazolyl ring. Moreover, the emission of 1
(502 nm) shows a blue-shift of 26 nm, relative to that of 4 (528
nm), because of the introduction of an electron-donating
methyl group into the 2-pyridyl ring of 1, which raises the
energy level of LUMO and thus gives an enlarged HOMO−
LUMO gap and a higher energy of emission.12 For 1−3 with a
different position of methyl group on the 2-pyridyl ring, the
emission peak shifts toward higher energy with λmax ≈ 520 nm
for 2, 517 nm for 3, and 502 nm for 1, which agrees with the
emission energy alteration of methylated 3-(2′-pyridyl)-1,2,4-
triazole ligands in CH2Cl2 solution (m-fmptzH (433 nm) < p-
fmptzH (422 nm) < o-fmptzH (417 nm)), indicating that the
methyl position on the 2-pyridyl ring has a similar influence on
the emissions of three methylated 3-(2′-pyridyl)-1,2,4-triazole
DOI: 10.1021/acs.inorgchem.7b01159
Inorg. Chem. 2017, 56, 10311−10324
Inorganic Chemistry Article

Figure 7. Emission spectra of complexes 1−3 in CH2Cl2 solution at Figure 9. Emission spectra of complexes 1−3 in the solid state at
ambient temperature. ambient temperature.

Figure 8. Emission spectra of complexes 1, 4, and 5 in CH2Cl2 Figure 10. Emission spectra of complexes 1, 4, and 5 in the solid state
solution at ambient temperature. at ambient temperature.

ligands (o-fmptzH, m-fmptzH, and p-fmptzH) and their

corresponding dinuclear Cu(I) complexes 1−3. By comparing
to that of 4 (528 nm), the introduction of methyl group into 2-
pyridyl ring makes the emissions of 1−3 blue-shift, as a result of
the elevation of the LUMO level.
The solid-state emission spectra of 1−5 at room temperature
(Figures 9 and 10) and at 77 K (Figures 11 and 12) were
investigated using powder samples, and pertinent emission data
are collected in Table 3. It is found that these dinuclear Cu(I)
complexes 1−5 are highly emissive in the solid state at room
temperature and display broad and unstructured emission band
peaking at 481, 493, 495, 499, and 494 nm with the emission
quantum yields of 0.406, 0.460, 0.806, 0.618, and 0.755,
respectively. The solid-state emission maxima are blue-shifted
to some degree, compared to their respective solution states, as
a consequence of the rigid medium.8k,10f,12 The variation trend
of solid emission maxima of 1, 4, and 5 are in agreement with
that of the solution emission maxima (1 < 5 < 4) and the solid- Figure 11. Emission spectra of complexes 1−3 in the solid state at 77
state emissions of 1−3 are also blue-shifted to different degree, K.
relative to that of 4, which is in good accordance with their
solution emissions. Moreover, the solid-state emission of 1 is
also markedly blue-shifted, relative to those of 2 and 3, which is the solid-state emission of 2 displays a blue-shift of 2 nm,
in good agreement with their solution emissions. Interestingly, whereas its solution emission gives a red-shift of 3 nm,
10318 DOI: 10.1021/acs.inorgchem.7b01159
Inorg. Chem. 2017, 56, 10311−10324
Inorganic Chemistry Article

and 1.58 V) of two 5-trifluoromethyl-3-(2′-pyridyl)-1,2,4-

Figure 12. Emission spectra of complexes 1, 4, and 5 in the solid state
at 77 K.
compared to those of 3. Such an anomaly can be rationalized in
terms of the smaller P1−Cu1−P3 angle (113.89(5)°) of 3
relative to that of 2 (130.02(5)°) in the solid state, resulting in
a lower energy of emission, as supported by the relationship
between the emission and the P−Cu−P angle.12a,29
Upon cooling to 77 K, the solid-state emissions of 1−5 show
a red shift of 18−25 nm, with respect to those at ambient
temperature, accompanied by a remarkable increase of emission
lifetimes (115−322 μs). This is a common emission behavior
for Cu(I) complexes with a small singlet−triplet energy gap
ΔE(S1−T1) and is often attributable to a large reduction of
thermally activated delayed fluorescence
(TADF).5b,6d,7a,d,8j,9d,e,g,30 Substantially, thermally activated
delayed fluorescence with larger radiative rate constant can be
suppressed at low temperature, and, thus, a red-shifted and
longer-lived emission can generally be presented.
The electrochemical properties of 1−4, but not those of the
poorly soluble 5, have been determined by cyclic voltammetry
in dry CH2Cl2, using ferrocene as the internal standard, and the
redox data are given in Table 3. In the anodic region, complexes
1−4 give an irreversible oxidation with the Epa value of ∼1.65,
1.54, 1.59, and 1.58 V, respectively, comparable to those (1.61
triazole-based Cu(I) triphenylphosphine complexes,12a which
can be attributed to the oxidation of Cu(I) to Cu(II).5f,11g,12a
Their oxidation potentials follow a ranking of 1 (1.65 V) > 3
(1.59 V) > 2 (1.54 V), indicating that the HOMO is affected by
the methyl position on the 2-pyridyl ring and involves some
contribution of functionalized 3-(2′-pyridyl)-1,2,4-triazole, as
suggested by TDDFT calculations. Moreover, the fairly high
oxidation potentials of the Cu(I) centers indicate a good
stabilization of these bimetallic Cu(I) species.5f,11g,12a
Theoretical Investigations. To further understand the
photophysical properties of the 3-(2′-pyridyl)-1,2,4-triazole-
based bimetallic Cu(I) complexes, the TDDFT/PBE1PBE
calculations of three typical Cu(I) complexes 1, 4, and 5 were
performed. The calculated lowest-lying absorption and
emission transition properties of 1, 4, and 5 in CH2Cl2 media
are summarized in Table 4. The frontier molecular orbitals
involved in the lowest-lying electronic absorption transitions of
1, 4, and 5 are shown in Figure 13. More tables and figures on
the TDDFT calculations are given in the Supporting
Information (see Tables S1−S9 and Figures S9−S15 in the
Supporting Information).
As depicted in Table S1 in the Supporting Information,
Figure 13, and Figure S10 in the Supporting Information, the
LUMO of 1 is largely localized on the monoanionic o-fmptz
ligand (85.82%), while its HOMO, HOMO-1, HOMO-2, and
HOMO-3 basically reside on Cu (45.08%−57.48%), dppm
(25.35%−39.99%), and o-fmptz (13.22%−23.81%). Therefore,
the calculated lowest-energy absorption of 1 at 326 nm (see
Tables 4 and S2) is a mixed 1MLCT/1LLCT/1IL (Cu/dppm/o-
fmptz→o-fmptz) state, which is dominated by the HOMO/
HOMO−1/HOMO−2/HOMO−3→LUMO transitions
(98%). Similar observations were detected for 2 and 3.
Moreover, the HOMO−1 of the NH-deprotonated complex
4 containing no methyl substituent on the 2-pyridyl ring (see
Table S3 in the Supporting Information, Figure 13, and Figure
S11 in the Supporting Information) is primarily composed of
two Cu(I) atoms (59.09%), with some contributions from two
dppm ligands (18.32%) and one monoanionic fptz chelate
(22.60%), while its LUMO is essentially located on the fptz
ligand (90.11%). Thus, the calculated lowest-energy absorption
at 332 nm for 4 (see Table 4 and Table S4 in the Supporting

Table 4. Absorption and Emission Transitions for 1, 4, and 5 in CH2Cl2 Solution Calculated by TDDFT Method at the
PBE1PBE Level

complex state transition (contribution) E [nm] (eV) oscillator strength assignment

1 T1 HOMO → LUMO (70%) 531 (2.33) 0 3
IL/ MLCT/3LLCT
3

HOMO-4 → LUMO (12%)

S1 HOMO → LUMO (41%) 326 (3.80) 0.0022 1
MLCT/1LLCT/1IL
HOMO-2 → LUMO (24%)
HOMO-1 → LUMO (23%)
HOMO-3 → LUMO (10%)

4 T1 HOMO → LUMO (47%) 555 (2.23) 0 3

LLCT/3IL/3MLCT
HOMO-5 → LUMO (29%)
HOMO-1 → LUMO (14%)
S1 HOMO-1 → LUMO (87%) 332 (3.70) 0.0020 1
MLCT/1IL/1LLCT

5 T1 HOMO → LUMO (93%) 627 (1.98) 0 3

MLCT/3LLCT/3IL
S1 HOMO-3 → LUMO (47%) 354 (3.51) 0.0040 1
MLCT/1IL/1LLCT
HOMO-1 → LUMO (38%)

10319 DOI: 10.1021/acs.inorgchem.7b01159

Inorg. Chem. 2017, 56, 10311−10324
Inorganic Chemistry
Figure 13. Plots of frontier molecular orbitals involved in the lowest-lying electronic absorption transitions of 1, 4, and 5.
Information) is also ascribed to a mixed 1MLCT/1IL/1LLCT
(Cu/fptz/dppm→fptz) character, which is mainly from the
HOMO-1 → LUMO transition (87%). For the NH-undeproto-
nated Cu(I) species 5 with a strong electron-donating tert-butyl
on the 1,2,4-triazolyl ring (see Table S5 in the Supporting
Information, Figure 13, and Figure S12 in the Supporting
Information), the LUMO is predominantly centered on
bmptzH (92.27%), while its HOMO-1 and HOMO-3 are
mainly distributed on Cu (48.39% and 65.41%), dppm (40.55%
and 16.43%), and bmptzH (11.06% and 18.16%). Hence, the
calculated lowest-energy absorption at 354 nm for 5 (see Table
4 and Table S6 in the Supporting Information), which
originates from the HOMO-3/HOMO-1 → LUMO transitions
(85%), is typical of 1MLCT (Cu → bmptzH) state mixed with
a certain degree of the 1LLCT (dppm → bmptzH) and 1IL
(bmptzH intraligand) properties. From the HOMO-n
compositions involved in the calculated lowest-lying absorption
transitions of 1, 4, and 5 (see Tables S1−S6), it is suggested
that the NH deprotonation of the 1,2,4-triazolyl ring not only
influences the contribution of functionalized 3-(2′-pyridyl)-
1,2,4-triazole on the HOMO-n in the ground state but also
increases the 1IL character of the lowest-energy absorption.
The emission properties of 1, 4, and 5 in CH2Cl2 media were
also investigated by TDDFT/PBE1PBE calculations, based on
the optimized lowest-energy triplet excited-state T1 geometries.
As depicted in Table 4 and Tables S7−S9, the calculated
lowest-energy triplet emissive state of the NH-deprotonated
complex 1 possessing a methyl group on the pyridyl ring, which
is largely from the HOMO → LUMO (70%) and HOMO-4 →
LUMO (12%) transitions, can be assigned to a mixed
3
IL/3MLCT/3LLCT character. Similarly, the calculated T1
state of the NH-deprotonated complex 4 without a methyl
substituent on the pyridyl ring, mainly from the HOMO/
HOMO-1/HOMO-5 → LUMO (90%) transitions, is attribut-
able to a mixed 3LLCT/3IL/3MLCT feature. However, the
calculated T1 state of the NH-undeprotonated complex 5 with a
tert-butyl group on the 1,2,4-triazolyl ring, which is almost from
the HOMO → LUMO (93%) transition, shows an appreciable
3
MLCT (Cu → bmptzH) character mixed with some 3LLCT
(dppm → bmptzH) and a small amount of the intra-bmptzH
10320
Article
(3IL) characters. From the HOMO-n compositions involved in
the calculated lowest-energy triplet emission transitions of 1, 4,
and 5 (see Tables S7−S9 and Figures S13−S15 in the
Supporting Information), the N−H deprotonation of the 1,2,4-
triazolyl ring not only affects the contribution of functionalized
3-(2′-pyridyl)-1,2,4-triazole ligand on the HOMO-n, but also
increases the 3IL character of the lowest-lying triplet emissions.
■
CONCLUSIONS
We have successfully designed and synthesized a new series of
luminescent three- and four-coordinate bimetallic Cu(I)
complexes 1−5 triply bridged by two bis(diphenylphosphino)-
methane ligands and a monoanionic or charge-neutral
functionalized 3-(2′-pyridyl)-1,2,4-triazole ligand in a special
μ−η1(N),η2(N,N) tridentate coordination mode. Their struc-
tural features and photophysical properties have been well-
investigated, and these dinuclear Cu(I) complexes are
considerably air-stable both in solution and in the solid state.
All of the complexes 1−5 exhibit good luminescence properties
in both solution and solid states at ambient temperature, and
their emission properties can be well-modulated via structural
modification of 3-(2′-pyridyl)-1,2,4-triazole including the
alteration of the substituent type (−CF3, −H, −CH3, and
−C(CH3)3) and position (ortho-, meta-, and para-position). It
is demonstrated that the introduction of the electron-donating
substituent into the 2-pyridyl ring leads to the blue shift of the
emission and the substituent at the ortho-position of the 2-
pyridyl ring exerts the most significant impact on the emission
wavelength, whereas introducing the electron-donating sub-
stituent to the 1,2,4-triazolyl ring results in a red-shifted
emission. In addition, the variation of the electronic nature of
the substituent on the 1,2,4-triazolyl ring markedly affects the
proton activity of the 1,2,4-triazolyl-NH and thus leads to the
formation of singly and doubly charged bimetallic Cu(I) species
originating from the NH ↔ N− conversion of the 1,2,4-triazolyl
ring. The results presented herein might provide a new insight
into the design and synthesis of the 3-(2′-pyridyl)-1,2,4-
triazole-based emissive dinuclear copper(I) complexes with
potentially high luminescence efficiency.
DOI: 10.1021/acs.inorgchem.7b01159
Inorg. Chem. 2017, 56, 10311−10324
Inorganic Chemistry
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.inorg-
chem.7b01159.
Characterization data of 1−5, and tables and figures
regarding the TDDFT calculations of 1, 4, and 5 (PDF)
Accession Codes
CCDC 1548396−1548400 contain the supplementary crystal-
lographic data for this paper (crystallographic data for 1−5).
These data can be obtained free of charge via the Internet
(www.ccdc.cam.ac.uk/data_request/cif), by E-mail (data_
request@ccdc.cam.ac.uk), or by contacting The Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge CB2
1EZ, UK (fax: +44 1223 336033).
■
AUTHOR INFORMATION
Corresponding Authors
*E-mail: gzchenjinglin@126.com (J.-L. Chen).
*E-mail: clamho@hkbu.edu.hk (C.-L. Ho).
*E-mail: jy_wang@fjirsm.ac.cn (J.-Y. Wang).
*E-mail: wai-yeung.wong@polyu.edu.hk (W.-Y. Wong).
ORCID
Jing-Lin Chen: 0000-0002-1973-9273
Cheuk-Lam Ho: 0000-0001-8596-0307
Sui-Jun Liu: 0000-0002-7705-0634
Wai-Yeung Wong: 0000-0002-9949-7525
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work was supported by the National Natural Science
Foundation of China (Nos. 21561013 and 21501077), the
Major Program of Jiangxi Provincial Natural Science
Fo undat io n of China for Yo un g Sch olar (Nos.
20143ACB21017 and 20161ACB21013), the Jiangxi Provincial
Natural Science Foundation of China (Nos. 20171BAB203005,
20171BCB23066, and 20151BAB213003) and the Program for
Qingjiang Excellent Young Talents, JXUST. W.-Y.W. thanks
The Hong Kong Polytechnic University (1-ZE1C) and the
Areas of Excellence Scheme of HKSAR (No. A0E/P-03/08) for
the financial support. C.-L.H. thanks the National Natural
Science Foundation of China (No. 21504074) and the Science,
Technology and Innovation Committee of Shenzhen Munic-
ipality (No. JCYJ20160531193836532) for the financial
support.
■
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10324 DOI: 10.1021/acs.inorgchem.7b01159

Inorg. Chem. 2017, 56, 10311−10324