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

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

Inorg. Chem. 2017, 56, 10311−10324
Inorganic Chemistry Article

in their OLEDs.10 Furthermore, it is also notable that the Chart 1

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. gave light yellow crystals of 1 (44.2 mg, 0.036 mmol, 72%). 1H NMR
Compared to mononuclear and multinuclear Cu(I) systems, (CD2Cl2, 400 MHz): δ 8.12 (d, 1H, J = 8 Hz), 7.83 (t, 1H, J = 6 Hz),
photoactive bimetallic Cu(I) species have been less studied, 7.45 (s, 2H), 7.38 (d, 2H, J = 4 Hz), 7.30−7.13 (m, 26H), 7.02 (d, 3H,
especially those bearing the Cu2(μ-dppm)2 core. Among the J = 8 Hz), 6.80 (s, 4H), 6.55 (s, 4H), 3.41 (s, 2H), 3.16 (s, 2H), 1.87
Cu2(μ-dppm)2-based system,11 the two Cu(I) centers all being (s, 3H). 31P NMR (CD2Cl2, 202.3 MHz): δ −9.55 (s, 2P, dppm),
four-coordinate are the most common and the two Cu(I) ions −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
all being three-coordinate can also be often seen,11c−l whereas (KBr, cm−1): 1096 vs (ClO4−).
three- and four-coordinate dinuclear Cu(I) complexes have Preparation of [Cu2(μ-dppm)2(μ−η1(N),η2(N,N)-m-fmptz)](ClO4)
been scarcely reported,11b,m−q only including a polydentate (2). Complex 2 was similarly prepared according to the procedure for
diimine-based dicopper(I) complex.11b As a continuation of our 1 by using [Cu(CH3CN)4](ClO4), m-fmptzH, and dppm. Light yellow
work in the 1,2,4-triazole-based Cu(I) coordination chem- crystals were obtained by slow diffusion of n-hexane into a
istry,12 it is expected that polydentate 3-(2′-pyridyl)-1,2,4- CH3COCH3/CH2Cl2 (v/v, 1:5) mixture of 2 (yield: 70%). 1H
triazole ligand can be incorporated into the [Cu2(μ-dppm)2]2+ NMR (CD2Cl2, 400 MHz): δ 8.16 (d, 1H, J = 8 Hz), 7.87 (s, 1H),
component to develop new emissive molecular materials based 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),
on dinuclear Cu(I) complexes. More interestingly, in this study, 6.59 (s, 4H), 3.32 (s, 4H), 2.16 (s, 3H). 31P NMR (CD2Cl2, 202.3
it is found that the functionalized 3-(2′-pyridyl)-1,2,4-triazole MHz): δ −11.05 (s, 4P, dppm). Anal. Calcd for
ligand can coordinate with the [Cu2(μ-dppm)2]2+ unit using an C59H50ClCu2F3N4O4P4: C, 57.97; H, 4.12; N, 4.58. Found: C,
unexpected μ−η1(N),η2(N,N) tridentate coordination mode 57.92; H, 4.14; N, 4.63. Selected IR (KBr, cm−1): 1095 vs (ClO4−).
instead of a common η2(N,N) bidentate chelating manner. Preparation of [Cu2(μ-dppm)2(μ−η1(N),η2(N,N)-p-fmptz)](ClO4)
Moreover, to the best of our knowledge, this type of three- and (3). Complex 3 was similarly prepared according to the procedure
four-coordinate dinuclear copper(I) complexes triply bridged for 1 by using [Cu(CH3CN)4](ClO4), p-fmptzH, and dppm. Light
by functionalized 3-(2′-pyridyl)-1,2,4-triazole and diphosphine 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
mixed ligands have not been reported hitherto. We describe
(CD2Cl2, 400 MHz): δ 8.15 (s, 1H), 8.13−8.08 (m, 1H), 7.34−7.07
herein the synthesis, characterization, and luminescence (m, 27H), 7.01−6.94 (m, 6H), 6.73 (t, 4H, J = 8 Hz), 6.53 (s, 4H),
properties of a new series of three- and four-coordinate 3.29 (s, 4H), 2.47 (s, 3H). 31P NMR (CD2Cl2, 202.3 MHz): δ −12.82
bimetallic copper(I) complexes triply bridged by two dppm (s, 4P, dppm). Anal. Calcd for C59H50ClCu2F3N4O4P4: C, 57.97; H,
ligands and a monoanionic or charge-neutral functionalized 3- 4.12; N, 4.58. Found: C, 58.01; H, 4.15; N, 4.55. Selected IR (KBr,
(2′-pyridyl)-1,2,4-triazole ligand in a μ−η1(N),η2(N,N) triden- cm−1): 1096 vs (ClO4−).
tate binding mode. 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
EXPERIMENTAL SECTION were isolated by the slow diffusion of petroleum ether into a
General Procedures and Materials. All reactions were CH3COCH3/CH2Cl2 (v/v, 1:5) mixture of 4 (yield: 75%). 1H NMR
performed under a N2 atmosphere using anhydrous solvents or (CD2Cl2, 400 MHz): δ 8.31 (d, 1H, J = 4 Hz), 8.24−8.19 (m, 1H),
solvents treated with an appropriate drying reagent. Commercially 7.96 (t, 1H, J = 6 Hz), 7.31−6.99 (m, 34H), 6.76 (s, 4H), 6.57 (s, 4H),
available reagents were used without further purification, unless 3.36 (s, 4H). 31P NMR (CD2Cl2, 202.3 MHz): δ −11.35 (s, 4P,
otherwise stated. Different functionalized 3-(2′-pyridyl)-1,2,4-triazole dppm). Anal. Calcd for C58H48ClCu2F3N4O4P4: C, 57.65; H, 4.00; N,
ligands including 5-trifluoromethyl-3-(6′-methyl-2′-pyridyl)-1H-1,2,4- 4.64. Found: C, 57.68; H, 4.03; N, 4.62. Selected IR (KBr, cm−1):
triazole (o-fmptzH), 5-trifluoromethyl-3-(5′-methyl-2′-pyridyl)-1H- 1095 vs (ClO4−).
1,2,4-triazole (m-fmptzH), 5-trifluoromethyl-3-(4′-methyl-2′-pyridyl)- Preparation of [Cu2(μ-dppm)2 (μ−η1(N),η2(N,N)-o-bmptzH)]-
1H-1,2,4-triazole (p-fmptzH), 5-trifluoromethyl-3-(2′-pyridyl)-1H- (ClO4)2 (5). Complex 5 was similarly prepared according to the
1,2,4-triazole (fptzH), and 5-tert-butyl-3-(6′-methyl-2′-pyridyl)-1H- procedure for 1 by using [Cu(CH3CN)4](ClO4), o-bmptzH, and
1,2,4-triazole (o-bmptzH) were synthesized using previously reported dppm. Colorless crystals were obtained by slow diffusion of petroleum
procedures.13 Chart 1 shows the structures of these ligands. ether into a CH3OH/CHCl3 (v/v, 1:5) mixture of 5 (yield: 83%).
Caution! Perchlorate salts are potentially explosive and should be Anal. Calcd for C62H60Cl2Cu2N4O8P4: C, 56.80; H, 4.61; N, 4.27.
handled caref ully in small amount. Found: C, 56.84; H, 4.58; N, 4.25. Selected IR (KBr, cm−1): 1098 vs
Preparation of [Cu2(μ-dppm)2(μ−η1(N),η2(N,N)-o-fmptz)](ClO4) (ClO4−).
(1). An admixture of [Cu(CH3CN)4](ClO4) (33.2 mg, 0.101 mmol) Crystal Structural Determination. Crystal data of 1−5 were
and o-fmptzH (11.5 mg, 0.050 mmol) in CH2Cl2 (5 mL) was stirred collected on a Bruker D8 QUEST diffractometer with graphite-
for 30 min at room temperature; dppm (39.2 mg, 0.102 mmol) was monochromated Mo Kα radiation (λ = 0.71073 Å). The program
then added and the mixture was stirred for another 2 h to get a light SAINT was used for integration of the diffraction profiles. Structures
yellow solution. The solvent was evaporated to dryness under reduced were solved by direct methods and refined by full-matrix least-squares
pressure. The residue was then dissolved in CH2ClCH2Cl/CH2Cl2 (v/ technique on F2 using the SHELXTL software package.14 Scheme 1
v, 1:5), and slow diffusion of petroleum ether into the above mixture shows depictions of these structures. The heavy atoms were located

10312 DOI: 10.1021/acs.inorgchem.7b01159

Inorg. Chem. 2017, 56, 10311−10324
Inorganic Chemistry Article

Scheme 1. Structures of Bimetallic Cu(I) Complexes 1−5

from E-map and other non-hydrogen atoms were found in subsequent state S0 and lowest-energy triplet excited-state T1 geometries. The
difference Fourier syntheses. All non-hydrogen atoms were refined solvent effects in CH2Cl2 media were taken into account by
anisotropically, while hydrogen atoms were generated geometrically performing the self-consistent reaction field (SCRF) calculations,
with isotropic thermal parameters. using the polarizable continuum model method (PCM).20 In these
Physical Measurements. 1H and 31P NMR spectra were recorded calculations, the Stuttgart−Dresden basis set21 consisting of the
on Bruker Avance III (400 MHz) NMR spectrometer with SiMe4 as effective core potentials (ECP) was employed for the Cu and P atoms,
the internal reference. Infrared (IR) spectra were collected on a Bruker and 6-31G(p,d) basis set22 for the remaining atoms were used.
Optics ALPHA FT-IR spectrometer using KBr pellets. Elemental Visualization of the frontier molecular orbitals was performed by
analyses (C, H and N) were conducted on a PerkinElmer Model 240C GaussView. The Ros and Schuit method (C-squared population
elemental analyzer, where all the crystal samples were used after analysis method, SCPA)23 is supported to analyze the partition orbital
grinding and drying under vacuum. Ultraviolet-visible light (UV-vis) composition by using Multiwfn 3.3.8 program.24

■
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 RESULTS AND DISCUSSION
fluorescence spectrometer (Edinburgh, Model F900) with a thermo- Syntheses and Characterizations. Dinuclear Cu(I)
electrically cooled photomultiplier tube (Hamamatsu, Model R3809). complexes 1−5 were prepared by treating [Cu(CH3CN)4]-
The luminescence quantum yields (Φem) in CH2Cl2 solution at (ClO4) with the corresponding functionalized 3-(2′-pyridyl)-
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
1,2,4-triazole (o-fmptzH, m-fmptzH, p-fmptzH, fptzH, and o-
subscripts “r” and “s” denote the reference standard and the sample bmptzH) and dppm in a 2:1:2 molar ratio. Complexes 1−4 are
solution, respectively, and n, D, and Φ are the refractive index of the readily soluble in CH2Cl2, CHCl3, and CH2ClCH2Cl, whereas
solvents, the integrated intensity, and the luminescence quantum yield, complex 5 shows poor solubility in common organic solvents
respectively.15 The quantity B is calculated by B = 1−10−AL, where A is including DMSO and DMF. In the 1H NMR spectra of 1−4 in
the absorbance at the excitation wavelength and L is the optical path CD2Cl2, besides the aromatic proton signals (δ 8.31−6.53
length. An integrating sphere (Lab sphere) was applied to measure the ppm) and the C−H resonances of the methylene (δ 3.41−3.16
luminescence quantum yield in the solid state. The cyclic voltammo- ppm) and methyl (δ 2.47−1.87 ppm) groups, the characteristic
grams were obtained with a potential/galvanostat analyzer (Princeton
N−H proton signal of the 1,2,4-triazolyl ring was not observed,
Applied Research, Model 263A), using a standard three-electrode
setup consisting of a glassy carbon disk working electrode, a platinum indicating that functionalized 3-(2′-pyridyl)-1,2,4-triazole ligand
counter electrode, and a Ag/AgCl reference electrode. All the with a trifluoromethyl group easily undergoes the 1,2,4-
experiments were carried out in dry and nitrogen-saturated CH2Cl2 triazolyl-NH deprotonation and coordinates to the Cu(I) ion
solutions with 0.1 M n-tertrabutylammonium hexafluorophosphate as as a monoanionic ligand, as supported by X-ray crystallography
the supporting electrolyte. The potentials are quoted versus the (vide infra). The methylene protons of two dppm (PCH2P)
ferrocenium/ferrocene couple (Fc+/0 = 0.51 V). ligands display two unresolved broad singlet peaks at 3.41 and
Computational Methodology. All the calculations were carried 3.16 ppm for 1, while only one unresolved broad singlet peak is
out by using the Gaussian 09 program package16 to gain an insight into detected at 3.32, 3.29, and 3.36 ppm for 2, 3, and 4,
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 respectively,11c−h which are closely related to the (ABXX′)2 or
theory (DFT)17 method at the restricted and unrestricted gradient (ABX2)2 spin system of the two sets of chemically inequivalent
corrected correlation functional PBE1PBE18 levels, respectively, was protons (CHaHbPP′ or CHaHbP2) in the Cu2(μ-dppm)2-based
used to optimize the ground state (S0) and the lowest-energy triplet complexes.11c,d Similarly, the 31P NMR spectra exhibit two
excited state (T1) geometries of complexes 1, 4, and 5 without unresolved broad peaks at −9.55 and −10.92 ppm for 1 and
symmetry constraint. The initial structures were extracted from the only one unresolved broad singlet peak at −11.05, −12.82, and
crystallographically determined geometries. During the optimization −11.35 ppm for 2, 3, and 4, respectively,11c−h which are
processes, the convergent values of maximum force, root-mean-square associated with the variation of the difference of the two
(RMS) force, maximum displacement, and RMS displacement were
set by default. To analyze the spectroscopic properties, 80 singlet
chemically inequivalent P atoms (CuPCHaHbP′Cu′) in the
excited states and 6 triplet excited states for 1, 4, and 5 in CH2Cl2 Cu2(μ-dppm)2-based complexes,11c,d as supported by the larger
solution were calculated by the time-dependent density functional difference of the Cu1−N1 and Cu2−N3 bond lengths of 1
theory (TDDFT)19 method at the same functional used in the (0.221 Å) caused by the ortho-methyl group, with respect to
geometrical optimization, respectively, based on the optimized ground- those of 2−4 (0.076−0.120 Å). On the other hand, these
10313 DOI: 10.1021/acs.inorgchem.7b01159
Inorg. Chem. 2017, 56, 10311−10324
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 further suggest that the substituent type and position on the 2-
spectra of 1 at room temperature can also be clearly observed in pyridyl ring have some impact on the coordination environ-
the variable-temperature 1H and 31P NMR spectra of the ment around the Cu(I) center, especially for the ortho-methyl
representative complex 2 in CD2Cl2 from 298 to 198 K (see group.
Figures S16 and S17 in the Supporting Information), The structures of 1−5 were established by single-crystal X-
suggesting the significant influence of the ortho-methyl ray diffraction. The crystallographic data and structure
substituent on the 2-pyridyl ring. Similarly, this signal refinement details of 1−5 are summarized in Table 1, and
coalescence phenomenon that the (PCH2P)2 system only selected bond lengths and angles are listed in Table 2.
exhibits an unresolved broad singlet peak in the 1H and 31P Complexes 1−4 with a trifluoromethyl group are all singly
NMR spectra of 2−4 at room temperature can also be well- charged bimetallic Cu(I) species with an eight-membered
presented in the variable-temperature 1H and 31P NMR spectra Cu2C2P4 ring of {Cu(μ-dppm)2Cu} unit, showing the chair−
of 1 in DMSO-d6 from 298 to 368 K (see Figures S18 and S19 boat conformation for 1 and 2 and the boat−boat form for 3
in the Supporting Information). Therefore, all these data and 4 (see Figures 1−4),11 in which these functionalized 5-
10314 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
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Inorganic Chemistry 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 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 = Figure 6. Absorption spectra of five free ligands and their
2,6-bis[4′-(S)-isopropyloxazolin-2′-yl]pyridine).11b For 1−5, corresponding complexes 1−5 in CH2Cl2 solution at ambient
the Cu1 center is located in a highly distorted P2N2 tetrahedral temperature.
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 triazole ligands exhibit multiple absorption bands in the UV
Cu1−Ntriazolyl lengths (2.044(6), 2.043(4), 2.017(4), 2.033(2), region (<310 nm) in CH2Cl2 solution, attributed to the ligand-
and 2.060(3) Å for 1−5, respectively) being much shorter than centered 1[π → π*] transitions. Their absorption spectra
the Cu1−Npyridyl lengths (2.236(7), 2.168(5), 2.159(4), display certain red-shifting (p-fmptzH < fptzH < m-fmptzH < o-
2.157(2), and 2.220(3) Å for 1−5, respectively), suggesting a fmptzH < o-bmptzH), because of the variation of the electron-
stronger bonding of Cu(I) to the N donor of the 1,2,4-triazolyl donating ability and position of the substituents on 3-(2′-
ring.12 The Cu2 center coordinates to the other two P atoms of pyridyl)-1,2,4-triazole. As depicted in Figure 6 and Table 3,
the two different dppm bridges and one N atom from the 1,2,4- these bimetallic Cu(I) complexes 1−5 display several
triazolyl moiety of 3-(2′-pyridyl)-1,2,4-triazole, in a distorted absorption peaks in the 230−320 nm region (ε > 104 M−1
P2N trigonal planar arrangement. It is noteworthy that the cm−1); those are attributable to the 1[π → π*] transitions of
Cu1−N1 and Cu1−N2 lengths of 4 are somewhat shorter, both functionalized 3-(2′-pyridyl)-1,2,4-triazole and dppm
whereas the Cu2−N3 distance is slightly longer, compared to ligands, which are somewhat red-shifted, because of the
those of 1−3, suggesting that the introduction of the methyl more-extended π-conjugation, compared to the five free
group into the 2-pyridyl ring exerts two different effects on the ligands. In addition, only comparatively weak low-energy
Cu1 and Cu2 cores. Moreover, the Cu−Npyridyl length of 5 is absorption tails (ε < 5500 M−1 cm−1) are observed in the
slightly shortened, whereas the Cu−Ntriazolyl distances are range of 320−400 nm for 1−5, suggesting that these weak low-
somewhat elongated, relative to those of 1, and the N−H energy absorptions are not markedly influenced by the
deprotonation occurring in 1 is not observed in 5, indicating functionalization of 3-(2′-pyridyl)-1,2,4-triazole.8k,12 As sug-
that the substituent type on the 1,2,4-triazolyl ring has two gested by TDDFT calculations (vide infra), the lowest-lying
diverse effects on the 2-pyridyl and 1,2,4-triazolyl moieties of electronic transitions of 1−5 are assigned to Cu/diphosphine
the functionalized 3-(2′-pyridyl)-1,2,4-triazole and the proton → diimine charge transfer (metal-to-ligand and ligand-to-ligand
activity of the 1,2,4-triazolyl-NH. For 1−3 with methyl group at charge transfer, 1MLCT/1LLCT) transitions, mixed with
different substituent positions, it is noted that the Cu1−N1 and different degrees of intraligand (1IL) charge transitions inside
Cu1−N2 lengths are decreased gradually (1 > 2 > 3), whereas functionalized 3-(2′-pyridyl)-1,2,4-triazole ligands.4,8k,11b−j,12
the Cu2−N3 distance is basically unchanged, except for that of As depicted in Figures 7 and 8, these dinuclear Cu(I)
1 due to the effect of the ortho-methyl group, implying that the complexes 1−5 show broad and unstructured emission band
methyl position at the 2-pyridyl ring has different effects on the peaking at 502, 520, 517, 528, and 520 nm with moderate
10316 DOI: 10.1021/acs.inorgchem.7b01159
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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, pronounced effect on the emission properties, relative to the
respectively, in degassed CH2Cl2 solution at ambient temper- introduction of a strong electron-withdrawing trifluoromethyl
ature. The luminescence intensity is drastically quenched by the group into the 1,2,4-triazolyl ring. Moreover, the emission of 1
presence of oxygen in aerated solution. Together with their (502 nm) shows a blue-shift of 26 nm, relative to that of 4 (528
relatively long luminescence lifetimes, from several to a dozen nm), because of the introduction of an electron-donating
microseconds, it is suggested that the emission may be methyl group into the 2-pyridyl ring of 1, which raises the
phosphorescent in origin.10f,12 The emission of 1 (502 nm) is energy level of LUMO and thus gives an enlarged HOMO−
blue-shifted by 18 nm, relative to that of 5 (520 nm), as a LUMO gap and a higher energy of emission.12 For 1−3 with a
consequence of the replacement of an electron-donating tert- different position of methyl group on the 2-pyridyl ring, the
butyl group on the 1,2,4-triazolyl ring by an electron- emission peak shifts toward higher energy with λmax ≈ 520 nm
withdrawing trifluoromethyl group, resulting in the 1,2,4- for 2, 517 nm for 3, and 502 nm for 1, which agrees with the
triazolyl-NH deprotonation of 1 and the negative charge of the emission energy alteration of methylated 3-(2′-pyridyl)-1,2,4-
1,2,4-triazolyl ring, which raises the energy level of LUMO and, triazole ligands in CH2Cl2 solution (m-fmptzH (433 nm) < p-
hence, enlarges the HOMO−LUMO energy gap and gives an fmptzH (422 nm) < o-fmptzH (417 nm)), indicating that the
emission with higher energy.8k,12 This also suggests that the methyl position on the 2-pyridyl ring has a similar influence on
deprotonation of the 1,2,4-triazolyl-NH would give a more the emissions of three methylated 3-(2′-pyridyl)-1,2,4-triazole
10317 DOI: 10.1021/acs.inorgchem.7b01159
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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
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Inorganic Chemistry Article

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

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

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Inorganic Chemistry Article

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 (3IL) characters. From the HOMO-n compositions involved in
(Cu/fptz/dppm→fptz) character, which is mainly from the the calculated lowest-energy triplet emission transitions of 1, 4,
HOMO-1 → LUMO transition (87%). For the NH-undeproto- and 5 (see Tables S7−S9 and Figures S13−S15 in the
nated Cu(I) species 5 with a strong electron-donating tert-butyl Supporting Information), the N−H deprotonation of the 1,2,4-
on the 1,2,4-triazolyl ring (see Table S5 in the Supporting triazolyl ring not only affects the contribution of functionalized
Information, Figure 13, and Figure S12 in the Supporting 3-(2′-pyridyl)-1,2,4-triazole ligand on the HOMO-n, but also
Information), the LUMO is predominantly centered on increases the 3IL character of the lowest-lying triplet emissions.

■
bmptzH (92.27%), while its HOMO-1 and HOMO-3 are
mainly distributed on Cu (48.39% and 65.41%), dppm (40.55% CONCLUSIONS
and 16.43%), and bmptzH (11.06% and 18.16%). Hence, the
calculated lowest-energy absorption at 354 nm for 5 (see Table We have successfully designed and synthesized a new series of
4 and Table S6 in the Supporting Information), which luminescent three- and four-coordinate bimetallic Cu(I)
originates from the HOMO-3/HOMO-1 → LUMO transitions complexes 1−5 triply bridged by two bis(diphenylphosphino)-
(85%), is typical of 1MLCT (Cu → bmptzH) state mixed with methane ligands and a monoanionic or charge-neutral
a certain degree of the 1LLCT (dppm → bmptzH) and 1IL functionalized 3-(2′-pyridyl)-1,2,4-triazole ligand in a special
(bmptzH intraligand) properties. From the HOMO-n μ−η1(N),η2(N,N) tridentate coordination mode. Their struc-
compositions involved in the calculated lowest-lying absorption tural features and photophysical properties have been well-
transitions of 1, 4, and 5 (see Tables S1−S6), it is suggested investigated, and these dinuclear Cu(I) complexes are
that the NH deprotonation of the 1,2,4-triazolyl ring not only considerably air-stable both in solution and in the solid state.
influences the contribution of functionalized 3-(2′-pyridyl)- All of the complexes 1−5 exhibit good luminescence properties
1,2,4-triazole on the HOMO-n in the ground state but also in both solution and solid states at ambient temperature, and
increases the 1IL character of the lowest-energy absorption. their emission properties can be well-modulated via structural
The emission properties of 1, 4, and 5 in CH2Cl2 media were modification of 3-(2′-pyridyl)-1,2,4-triazole including the
also investigated by TDDFT/PBE1PBE calculations, based on alteration of the substituent type (−CF3, −H, −CH3, and
the optimized lowest-energy triplet excited-state T1 geometries. −C(CH3)3) and position (ortho-, meta-, and para-position). It
As depicted in Table 4 and Tables S7−S9, the calculated is demonstrated that the introduction of the electron-donating
lowest-energy triplet emissive state of the NH-deprotonated substituent into the 2-pyridyl ring leads to the blue shift of the
complex 1 possessing a methyl group on the pyridyl ring, which emission and the substituent at the ortho-position of the 2-
is largely from the HOMO → LUMO (70%) and HOMO-4 → pyridyl ring exerts the most significant impact on the emission
LUMO (12%) transitions, can be assigned to a mixed wavelength, whereas introducing the electron-donating sub-
3
IL/3MLCT/3LLCT character. Similarly, the calculated T1 stituent to the 1,2,4-triazolyl ring results in a red-shifted
state of the NH-deprotonated complex 4 without a methyl emission. In addition, the variation of the electronic nature of
substituent on the pyridyl ring, mainly from the HOMO/ the substituent on the 1,2,4-triazolyl ring markedly affects the
HOMO-1/HOMO-5 → LUMO (90%) transitions, is attribut- proton activity of the 1,2,4-triazolyl-NH and thus leads to the
able to a mixed 3LLCT/3IL/3MLCT feature. However, the formation of singly and doubly charged bimetallic Cu(I) species
calculated T1 state of the NH-undeprotonated complex 5 with a originating from the NH ↔ N− conversion of the 1,2,4-triazolyl
tert-butyl group on the 1,2,4-triazolyl ring, which is almost from ring. The results presented herein might provide a new insight
the HOMO → LUMO (93%) transition, shows an appreciable into the design and synthesis of the 3-(2′-pyridyl)-1,2,4-
3
MLCT (Cu → bmptzH) character mixed with some 3LLCT triazole-based emissive dinuclear copper(I) complexes with
(dppm → bmptzH) and a small amount of the intra-bmptzH potentially high luminescence efficiency.
10320 DOI: 10.1021/acs.inorgchem.7b01159
Inorg. Chem. 2017, 56, 10311−10324
Inorganic Chemistry Article

■
*
ASSOCIATED CONTENT
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Application of Phosphorescent Iridium(III) Complex Systems. Adv.
Mater. 2009, 21, 4418−4441. (c) Chen, Z.-Q.; Bian, Z.-Q.; Huang, C.-
The Supporting Information is available free of charge on the H. Functional IrIII Complexes and Their Applications. Adv. Mater.
ACS Publications website at DOI: 10.1021/acs.inorg- 2010, 22, 1534−1539. (d) Zhao, Q.; Li, F.; Huang, C. Phosphorescent
chem.7b01159. chemosensors based on heavy-metal complexes. Chem. Soc. Rev. 2010,
Characterization data of 1−5, and tables and figures 39, 3007−3030. (e) Xiao, L.; Chen, Z.; Qu, B.; Luo, J.; Kong, S.;
regarding the TDDFT calculations of 1, 4, and 5 (PDF) Gong, Q.; Kido, J. Recent Progresses on Materials for Electro-
phosphorescent Organic Light-Emitting Devices. Adv. Mater. 2011, 23,
Accession Codes 926−952. (f) Ho, C.-L.; Yu, Z.-Q.; Wong, W.-Y. Multifunctional
CCDC 1548396−1548400 contain the supplementary crystal- polymetallaynes: properties, functions and applications. Chem. Soc. Rev.
lographic data for this paper (crystallographic data for 1−5). 2016, 45, 5264−5295.
These data can be obtained free of charge via the Internet (3) (a) Lamansky, S.; Djurovich, P.; Murphy, D.; Abdel-Razzaq, F.;
(www.ccdc.cam.ac.uk/data_request/cif), by E-mail (data_ Lee, H.-E.; Adachi, C.; Burrows, P. E.; Forrest, S. R.; Thompson, M. E.
[email protected]), or by contacting The Cambridge Highly Phosphorescent Bis-Cyclometalated Iridium Complexes:
Synthesis, Photophysical Characterization, and Use in Organic Light
Crystallographic Data Centre, 12 Union Road, Cambridge CB2 Emitting Diodes. J. Am. Chem. Soc. 2001, 123, 4304−4312.
1EZ, UK (fax: +44 1223 336033).

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(b) D’Andrade, B. W.; Thompson, M. E.; Forrest, S. R. Controlling
Exciton Diffusion in Multilayer White Phosphorescent Organic Light
AUTHOR INFORMATION Emitting Devices. Adv. Mater. 2002, 14, 147−151. (c) Tsuboyama, A.;
Corresponding Authors Iwawaki, H.; Furugori, M.; Mukaide, T.; Kamatani, J.; Igawa, S.;
*E-mail: [email protected] (J.-L. Chen). Moriyama, T.; Miura, S.; Takiguchi, T.; Okada, S.; Hoshino, M.; Ueno,
*E-mail: [email protected] (C.-L. Ho). K. Homoleptic Cyclometalated Iridium Complexes with Highly
*E-mail: [email protected] (J.-Y. Wang). Efficient Red Phosphorescence and Application to Organic Light-
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Qingjiang Excellent Young Talents, JXUST. W.-Y.W. thanks Photochemistry and Photophysics of Coordination Compounds: Copper,
The Hong Kong Polytechnic University (1-ZE1C) and the Photochemistry and Photophysics of Coordination Compounds I; Eds.;
Areas of Excellence Scheme of HKSAR (No. A0E/P-03/08) for Balzani, V.; Campagna, S., Eds.; Topics in Current Chemistry , Vols.
the financial support. C.-L.H. thanks the National Natural 280−281; Springer: Berlin, Heidelberg, Germany, 2007; pp 69−115.
Science Foundation of China (No. 21504074) and the Science, (b) Barbieri, A.; Accorsi, G.; Armaroli, N. Luminescent complexes
beyond the platinum group: the d10 avenue. Chem. Commun. 2008,
Technology and Innovation Committee of Shenzhen Munic- 2185−2193.
ipality (No. JCYJ20160531193836532) for the financial (5) (a) McMillin, D. R.; McNett, K. M. Photoprocesses of Copper
support.

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10324 DOI: 10.1021/acs.inorgchem.7b01159

Inorg. Chem. 2017, 56, 10311−10324