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Introduction
The photoluminescent properties of transition metal complexes
have garnered much attention due to their potential applications in
dye-sensitized solar cells, light-emitting or electrochemical devices
and photochemical catalysts.1,2 Searching for highly efcient
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Scheme 1
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Fig. 1 (a) An ORTEP view of 1a with 30% thermal ellipsoids, showing the local coordination environment of Cu+ . The dihedral angle between the
.
NCuN and PCuP planes is 90.5 . (b) The p p interaction of a pair of symmetry-related complexes with a ring centralcentral distance of 3.572 A
exist in the crystal lattices, but they are not discussed here. The
biphenyl moieties in 4a and 4b exhibit twisted conformations with
twist angles between phenyl rings of 34.3 and 26.3 , respectively.
But complexes with pbaa or pbbaa ligands exhibit relatively rigid
features.
Spectroscopic properties
phenyl amine moiety in 1a and 1b, maybe due to the relatively less
conjugated electrons of the phenyl amine moiety in pba. Of course,
the CH F contacts between complex cations and anions surely
Fig. 3 (a) An ORTEP view of 2a with 30% thermal ellipsoids, showing the local coordination environment of Cu+ . The dihedral angles between the
NCuN and PCuP planes around Cu1 and Cu2 are 97.4 and 97.4 , respectively. (b) The 1D chain structure constructed by intermolecular CH p
, H57 pcentroid = 2.984 A
).
interactions between arene amine rings and phenyl H atoms (H29 pcentroid = 2.908 A
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Fig. 4 (a) An ORTEP view of 2b with 30% thermal ellipsoids, showing the local coordination environment of Cu+ . The dihedral angle between the
NCuN and PCuP planes is 91.9 . (b) The 1D chain structure constructed by intermolecular CH p interactions between arene amine rings and phenyl
).
H atoms (H26 pcentroid = 2.868 A
Fig. 5 (a) An ORTEP view of 3a with 30% thermal ellipsoids, showing the local coordination environment of Cu+ . The dihedral angle between NCuN
and PCuP planes is 91.6 . (b) Showing 1D chain structure constructed by intermolecular CH p interactions between arene amine rings and phenyl
, H15 pcentroid = 2.566 A
).
H atoms (H59 pcentroid = 2.631 A
Fig. 6 (a) An ORTEP view of 3b with 30% thermal ellipsoids, showing the local coordination environment of Cu+ . The dihedral angle between the
NCuN and PCuP planes is 96.8 . (b) The intermolecular T-shaped structure induced by intermolecular CH p interactions between arene amine
, H40 pcentroid = 2.697 A
).
rings and phenyl H atoms (H38 pcentroid = 2.615 A
Fig. 7 (a) An ORTEP view of 4a with 30% thermal ellipsoids, showing the local coordination environment of Cu+ . The dihedral angles between the
NCuN and PCuP planes around Cu1 and Cu2 are 91.4 and 91.3 respectively. (b) The intermolecular T-shaped structure induced by intermolecular
, H70 pcentroid = 2.948 A
, H79 pcentroid = 2.797 A
).
CH p interactions between arene amine rings and phenyl H atoms (H67 pcentroid = 2.819 A
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Solid state
Complex
l max (nm)
U em
t (ms)
K r (s-1 )
1a
2a
3a
4a
1b
2b
3b
4b
412 (2400)
422 (5000)
425 (5200)
418 (4900)
397 (2900)
400 (6200)
389 (5200)
395 (3400)
620
618
610
612
637
615
596
583
0.00093
0.00215
0.00162
0.00991
0.00305
0.03520
0.31300
0.07150
4.14
6.77
5.56
8.15
7.55
14.90
18.95
15.21
2.25
3.18
1.54
1.21
4.04
2.36
1.65
4.50
knr (s-1 )
102
102
102
103
102
103
104
103
2.41
1.47
9.48
9.67
1.32
6.48
3.62
6.10
105
105
104
104
105
104
104
104
l max (nm)
t (ms)
563
582
572
595
513
529
566
589
19.95
15.82
15.83
14.57
50.94
34.28
28.57
14.82
Fig. 9 Contour plots of the HOMO (left) and LUMO (right) of complex
3b.
band. The reason for these is that bulky substituents can sterically
prevent structural relaxation in the MLCT states, and decrease
non-radiative decay. Furthermore, for complexes with identical
diimine but different phosphine ligands, the tendency toward an
increased lifetime, as well as for a blue-shifted emission, goes
with the decrease in size of the phosphine ligands. Intermolecular
CH p interactions can trigger vibrationally relaxed energy
transfer in the excited state, and subsequently result in nonradiative decay. A larger-sized central arene ring is favorable
for forming intermolecular CH p interactions (see the abovediscussed crystal structure). Therefore smaller-sized complexes
exhibit longer lifetimes and blue-shifted emissions in the solid
state due to less vibrationally relaxed behavior related to exible
CH p bonds. Complexes 4a and 4b exhibit the lowest intensity
luminescence and the shortest lifetime, maybe due to the biphenyl
moiety in dppaa, which can be rotated, enhancing the vibrationally
relaxed CT excited state.
This journal is The Royal Society of Chemistry 2011
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Experimental Section
General
rigid naphthalene ring exhibits the best emission with the largest
quantum yield (0.313) and the longest emission lifetime (18.95 ms).
The inuence of intermolecular interactions on luminescent
properties is much weaker in dilute solution. It should be noted
that complexes 4a and 4b have relatively better emissions in
solution, maybe due to the increasing coplanarity of two phenyl
rings in the biphenyl moiety in solution leading to extended
intraligand electron delocalization and minimized excited state
distortion of the corresponding complex.18 Nevertheless, the fact
that the emission of 4b is similar to 2b, but not as good as that of
rigid complex 3b, shows that the rotating/vibrating behavior of the
biphenyl moiety is still not ignored in solution. The emission yields
of our phen-complexes are similar to that of Cu(phen)(POP)]+ ,
but their lifetimes are longer than that of the latter. However, the
lifetimes of dmp complexes in our system are comparable with
those of [Cu(dmp)(POP)]+ or [Cu(dbp)(POP)]+ ,6a but the yields
are a little lower than those of the latter complexes. Complex 3b is
exceptional, its emission yield is higher than [Cu(dmp)(POP)]+ ,
even comparable with that of [Cu(POP)(DMPP)]+ (DMPP =
2,9-dimethyl-4,7-phenylphenanthroline), which was reported as
a good luminophore with the highest quantum yield in the
[Cu(NN)(PP)]+ system.19
The experimentally measured t and U values were used to
calculate the radiative, kr and the nonradiative, knr , rate constants.
The kr values of dmp complexes exhibit a marked increase with
size increase, but the knr values of phen complexes slightly decrease
with size increase, showing that the bulkiness of ligand preventing
complexes from distorting in the excited states plays a dominant
role in solution. The knr values of 2b and 4b are similar, though
their sizes are very different. The highest kr value, as well as the
low nonradiative decay of 3b results from the cooperative effects
of structural rigidity and steric encumbrance.
In conclusion, the crystal structures and photophysical properties of these eight complexes are discussed in detail. Results
show that the steric encumbrance of bulky substitutes in the 2
and 9 positions of phenanthroline plays a dominant role in the luminescent properties of the [Cu(NN)(PP)]+ system. Furthermore,
intermolecular CH p interactions have an inuence on the nal
7556 | Dalton Trans., 2011, 40, 75517558
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Yield: 0.032 g (76%). Anal. calcd for C46 H41 N3 BF4 P2 Cu: C, 65.09;
H, 4.83; N, 4.95. Found: C, 64.82; H, 4.91; N, 5.12. 1 H NMR
(CD3 SOCD3 , 25 C, TMS): d = 2.7 (6H, CH3 ), 5.3 (4H, CH2 ),
7.47.6 (5H, C6 H5 N), 7.77.9 (20H, C6 H5 P), 8.29.1 ppm (6H,
Hphen). 31 P{1 H}NMR (CDCl3 ): -19.83. ESIMS (+): m/z 761
[Cu(pda)(dmp)]+ .
Yield: 0.035 g (41%). Anal. calcd for C92 H80 N6 B2 F8 P4 Cu2 , C, 65.17;
H, 4.72; N, 4.96. Found: C, 65.52; H, 4.97; N, 5.05. 1 H NMR
(CD3 SOCD3 , 25 C, TMS): d = 2.42.5 (12H, CH3 ), 5.15.3 (8H,
CH2 ), 7.57.8 (8H, NC6 H4 C6 H4 N), 7.88.0 (40H, C6 H5 P),
8.29.1 ppm (12H, Hphen). 31 P{1 H}NMR (CDCl3 ): -20.77.
ESIMS (+): m/z 760 [Cu2 (dmp)2 (pnaa)]2+ . Single crystals were
collected by vapor diffusion of diethyl ether into DMF solution
of complex.
Acknowledgements
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