Synthesis, crystal structures, and electronic spectra of (1,8-naphthyridine)ReI(CO)3Cl and [(1,8-naphthyridine)CuI(DPEPhos)]PF6

Article abstract of DOI:10.1016/j.inoche.2007.09.010

Two 1,8-naphthyridine (nap) metal complexes (nap)Re^I(CO)₃Cl (1) and [(nap)Cu^I(DPEPhos)]PF₆ (2) were synthesized and characterized by NMR-, emission, and absorption spectroscopy, elemental analysis, mass spectrometry, and X-ray structural analysis. In both complexes, the nap ligand coordinates with both N atoms to the metal centre in a bidentate manner. 1 and 2 exhibit a broad phosphorescence in solid state at T = 300 K, which is completely quenched in solution at r.t. In addition, the gas-phase structures of both complexes were optimized at the B3LYP/6-31G(d,p) level of theory.

Full text of DOI:10.1016/j.inoche.2007.09.010

Available online at www.sciencedirect.com
Inorganic Chemistry Communications 10 (2007) 1473–1477
www.elsevier.com/locate/inoche
Synthesis, crystal structures, and electronic spectra
of (1,8-naphthyridine)ReI(CO)3Cl and
[(1,8-naphthyridine)CuI(DPEPhos)]PF6
a,
a
b
c
b
U. Monkowius *, Y.N. Svartsov , T. Fischer , M. Zabel , H. Yersin
a
Institut fu¨r Anorganische Chemie, Johannes Kepler Universita¨t Linz, A-4040 Linz, Austria
Institut fu¨r Physikalische Chemie, Universita¨t Regensburg, D-93053 Regensburg, Germany
Zentrale Analytik der Universita¨t Regensburg, Ro¨ntgenstrukturanalyse, D-93053 Regensburg, Germany
b
c
Received 10 August 2007; accepted 15 September 2007
Available online 26 October 2007
Abstract
Two 1,8-naphthyridine (nap) metal complexes (nap)ReI(CO)3Cl (1) and [(nap)CuI(DPEPhos)]PF6 (2) were synthesized and character-
ized by NMR-, emission, and absorption spectroscopy, elemental analysis, mass spectrometry, and X-ray structural analysis. In both
complexes, the nap ligand coordinates with both N atoms to the metal centre in a bidentate manner. 1 and 2 exhibit a broad phospho-
rescence in solid state at T = 300 K, which is completely quenched in solution at r.t. In addition, the gas-phase structures of both com-
plexes were optimized at the B3LYP/6-31G(d,p) level of theory.
ꢀ 2007 Elsevier B.V. All rights reserved.
Keywords: Naphthyridine; Rhenium; Copper; Electronic spectra; Photoluminescence
1,8-Naphthyridine (nap) is well established in coordina-
tion chemistry and a great number of metal complexes bear-
ing nap as ligand have been published previously [1,2]. Nap
and its derivatives can act as monodentate [3–6], bidentate
[5–8] and dinuclear bridging [3,5,9–11] ligands. Due to this
variability of binding and the ease of preparation, the nap
moiety is a versatile building block for several ligand sys-
tems [12–18] yielding complexes which display interesting
structural [3–10], magnetic, [9] luminescent, [17] catalytic
[11,19] and electrochemical [8,13,18,20] properties. For
instance, nap is frequently used as a bridging ligand in
RhI- and NiII-complexes, where a close metal contact is
achieved by the geometrical demand of the ligand. In the
monodentate binding pattern, the free N atom can act as
an additional reaction site for another ligand (e.g. CO
[8,20]) or for substrates during redox reactions. This enables
the pre-orientation of reaction partners during a catalytic
cycle, which could enhance the catalytic efficiency. Further-
more, nap easily interchanges between mono- and bidentate
coordination and thus can provide a free coordination site
at a catalytically active metal centre [8].
Nevertheless, little is known about the photophysical
properties of complexes containing the unsubstituted nap
ligand. To probe the ability to generate luminescent com-
pounds, two examples with (nap)ReI(CO)3Cl (1) and
[(nap)CuI(DPEPhos)]PF6 (2) (DPEPhos = bis[2-(diphenyl-
phosphino)phenyl]ether) were prepared and characterized.
Analogous complexes containing 1,10-phenanthroline
(phen) and 2,20-bipyridine (bpy) instead of nap have been
investigated thoroughly. They exhibit intense photo- and
electroluminescence and have demonstrated their applica-
bility in organic light emitting devices (OLEDs) [21–29].
*
Corresponding author. Tel.: +43 732 2468 8814; fax: +43 732 2468
N
N
N
N
N
N
2468.
phen
bpy
nap
E-mail address: uwe.monkowius@jku.at (U. Monkowius).
1387-7003/$ - see front matter ꢀ 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.inoche.2007.09.010

1474
U. Monkowius et al. / Inorganic Chemistry Communications 10 (2007) 1473–1477
Complex 1 was prepared from nap and Re(CO)5Cl in
boiling toluene in almost quantitative yields (Eq. (1)) [30].
The copper complex is obtained in good yields (76%) from
nap, DPEPhos and [Cu(NCMe)4]PF6 in DCM solution
(Eq. (2)) [31]. Both compounds are yellow powders and
are stable in the solid state and solutions under aerobic
conditions. Complex 1 is soluble in polar organic solvents
(MeCN, DCM, CHCl3), whereas complex 2 is only mod-
estly soluble in hot MeCN. Their identities were confirmed
by elemental analyses, mass spectrometry and NMR spec-
troscopy [30,31].
Fig. 1. Crystal structure of 1 (ORTEP drawing with 50% probability
+ Re(CO)5Cl
˚
ellipsoids). Selected bond lengths [A] and angles [ꢁ]: Re1–N1 2.232(3), Re1–
N
N
N2 2.236(2), Re1–Cl1 2.4937(8), Re1–C9 1.921(3), Re1–C10 1.929(4), Re1–
C11 1.915(3), N1–Re1–N2 60.12(10), N1–Re1–C11 105.28, C10–Re1–C11
87.89(15), Cl1–Re1–N1 83.33(6), Cl1–Re1–C9 176.27(10), Re1–N1–C1
95.1(2), Re1–N2–C1 94.91(17).
Cl
ð1Þ
CO
CO
N
N
toluene, Δ
Re
- 2 CO
97 %
CO
1
+ [Cu(NCMe)4]PF6
+
O
N
N
PPh2
PPh2
+
Ph
P
Ph
ð2Þ
_
PF6
CH2Cl2, r.t.
N
N
Cu+
O
- 4 MeCN
76 %
P
Ph
Ph
2
Single crystals of 1 suitable for structure determination
by X-ray diffraction were obtained from CHCl3/Et2O.
ꢀ
The compound crystallizes in the triclinic space group P1
with Z = 2 molecules in the unit cell [32]. Although the
complexes in crystals of 1 show no crystallographically
imposed symmetry, they closely approach a mirror symme-
try with a mirror plane including Re1, Cl1, and C9. Nap
acts as a bidentate ligand and the Re–N distances are
Fig. 2. Crystal structure of the cation in crystals of 2 (H atoms are omitted
˚
˚
for clarity). Selected bond lengths [A] and angles [ꢁ]: Cu1–N1 2.0254(15),
almost identical [2.232(3) and 2.236(2) A]. Thus, the Re(I)
Cu1–N2 2.5633(16), Cu1–P1 2.2426(5), Cu1–P2 2.2706(5), N1–Cu1–N2
58.31, P1–Cu1–P2 116.62(2), P1–Cu1–N1 127.31(4), Cu1–N1–C44
105.98(11), Cu1–N2–C44 82.34(10).
atom exists in a distorted octahedral environment defined
by a facial arrangement of the three carbonyl groups, the
chloride atom and the two nitrogen atoms of the nap
ligand (Fig. 1). The distortion from the ideal octahedral
symmetry essentially arises from the sterical demand of
the chelating nap ligand with its small bite angle.
length as well as of the Cu–N–C44 angles [<(Cu1–N1–
C44) 105.98(11)ꢁ, <(Cu1–N2–C44) 82.34(10)ꢁ] mark the
transition from a bidentate to a monodentate or bridging
coordination pattern of the nap ligand. By contrast, only
one set of protons (and only one phosphor species of the
DPEPhos ligand) is observed in the NMR spectra of 2,
showing a dynamic behaviour in solution equilibrating
the positions [3,5]. In fact, there are examples for a bridging
coordination geometry of the nap ligand in similar
copper complexes (e.g.[Cu2(nap)2(dppm)(MeCN)](PF6)2
with dppm = bis(diphenylphosphino)methane) [10]. The
Crystals of 2 obtained from MeCN/Et2O are triclinic,
ꢀ
with space group P1 ðZ ¼ 4Þ. The copper atom is coordi-
nated by nap and DPEPhos in a distorted tetrahedral envi-
ronment (Fig. 2). There are no sub-van der Waals contacts
between the oxygen of the phosphine ligand and the copper
centre. Whereas the Cu–P bond lengths are comparable
˚
˚
[Cu1–P1 2.2426(5) A, Cu1–P2 2.2706(5) A], the nap coor-
˚
dination is highly asymmetric [Cu1–N1 2.0254(15) A,
Cu1–N2 2.5633(16) A]. The differences of the Cu–N bond
˚

U. Monkowius et al. / Inorganic Chemistry Communications 10 (2007) 1473–1477
1475
˚
averaged Cu1–Nnap distance of 2.025(1) A of the latter
Typically, heteroleptic Cu(I) complexes containing
N \ N and DPEPhos ligands exhibit ligand centred fea-
tures in the UV and a broad MLCT band in the 350–
450 nm spectral range [23,25,26]. In compound 2 the sig-
nals in the UV spectral region appear at kmax = 301 and
224 nm (lge = 4.22, 4.80). In contrast to the known Cu(I)
complexes, a very weak low energy MLCT band occurs
in the usual MLCT absorption range (kmax = 380 nm,
lge = 1.87, not depicted in Fig. 5). The observed e value
seems to be too small for a typical singlet ground
complex is the same as the Cu1–N1 contact in 2. In [Cu(bp-
nap)(PPh3)2]PF6
(bpnap = 2,7-bis(2-pyridyl)-1,8-naph-
thyridine), the copper atom is also complexed by two
nitrogen atoms, one stemming from nap and the other
one from the pyridine moiety [14].
The nap ligand exhibits a structured absorption at
max = 297, 303, 308 nm (lge = 3.69, 3.74, 3.72) and
k
257 nm (lge = 3.63) in CHCl3 (Fig. S1), which is in
accordance with the published values [33]. Complex 1
exhibits the lowest energy band at kmax = 415 (lge = 3.25)
and transitions which appear near the free ligand absorp-
tion (kmax = 276, 301, 313 nm; lge = 4.18, 3.93, 3.79)
(Fig. 3). The lower energy absorption at 415 nm is assign-
able to a MLCT Re(dp)!nap(p*) transition. The higher
energy band can be associated with LC(p–p*) electronic
transitions localized mainly on the nap ligand. These two
absorption features are well known for Re(I) complexes
of the form ðN \ NÞReðCOÞ3Cl (N \ N e.g. 1,10-phenan-
throline, 2,20-bipyridine, etc.) [22]. In addition, DFT calcu-
lations confirm the interpretation that the highest occupied
molecular orbital (HOMO) is metal centred and the highest
unoccupied molecular orbital (LUMO) is ligand centred
(Fig. 4) [34].
1
state! MLCT transition, therefore further investigations
are required. Thus, although the substance is yellow in
the solid state the acetonitrile solution is colourless. A pos-
sible reason for this behaviour might be the transient
displacement of one of the nap’s nitrogen atoms by a sol-
vent molecule. The DFT calculation of the ground state
structure of 2 roughly reproduces the coordination mode
of the X-ray structure. The nap ligand is also coordinated
in an asymmetric, almost monodentate manner, but the
Cu–N and Cu–P bonds are too long (Fig. S2 and Table
S2). The difference in structures may be the result of a flat
potential surface for the nap coordination. Therefore, the
calculated results are not reliable to draw conclusion
regarding the electronic situation in the complex.
Fig. 3. Electronic absorption (in CHCl3 solution, left axis) and emission
Fig. 5. Electronic absorption (in MeCN solution, left axis) and emission
(solid state, 300 K, kexc = 400 nm, right axis) spectrum of [(nap)CuI-
(DPEPhos)]PF6.
(solid state, 300 K,
(nap)ReI(CO)3Cl.
kexc = 450 nm, right axis) spectrum of
Fig. 4. Contour plots of the highest occupied and lowest unoccupied molecular orbital (DFT calculation at the B3LYP/6-31G(d,p) level).

1476
U. Monkowius et al. / Inorganic Chemistry Communications 10 (2007) 1473–1477
M.J. Bermejo, J.I. Ruiz, X. Solans, J. Vinaixa, Inorg. Chem. 27
In chloroform solution at room temperature, the free
(1988) 4385;
nap ligand shows a structured blue emission at kem = 388
and 407 nm with shoulders on both the high and low
energy sides at 369 and 430 nm (Fig. S1). Complexes 1
and 2 exhibit a broad, structureless and weak emission
K.R. Dixon, Inorg. Chem. 16 (1977) 2618.
[4] T. Koizumi, K. Tanaka, Inorg. Chim. Acta 357 (2004) 3666;
W.P. Griffith, T.Y. Koh, A.J.P. White, D.J. Williams, Polyhedron 14
(1995) 2019.
[5] H. Nakajima, H. Nagao, K. Tanaka, Dalton Trans. (1996) 1405;
T. Suzuki, Inorg. Chim. Acta 359 (2006) 2431.
[6] M.J. Bermejo, J.I. Ruiz, X. Solans, J. Vinaixa, J. Organomet. Chem.
463 (1993) 143.
[7] A. Clearfield, P. Singh, I. Bernal, J. Chem. Soc. D – Chem. Commun.
(1970) 389;
in solid state at T = 300 K (1: kem = 594 nm; 2: kem
=
638 nm). Their emission decay times are in the microsecond
regime. These findings are well established for analogous
metal complexes and indicate phosphorescence from
3MLCT or MLCT perturbed 3LC states [22–27]. However,
the emissions of both complexes are completely quenched
in solution at room temperature. For 2, a nucleophilic
attack by oxygen at the copper centre is feasible because
DPEPhos is capable of functioning as a tridentate ligand
[35], but intramolecular exciplex quenching seems to be
improbable [26]. Furthermore, solvent-induced quenching
which involves a transient increase in the coordination
number of the copper centre is widely found for MLCT
states of Cu(I) complexes [27,28]. Nevertheless, for both
complexes the most likely mechanism is vibrational deacti-
vation of the excited state due to the fluxional behaviour of
the nap ligand. Even at a temperature of 77 K the emission
of 2 is completely quenched in acetonitrile, whereas 1
P. Singh, A. Clearfield, I. Bernal, J. Coord. Chem. 1 (1971) 29;
M.A. Cavanaugh, V.M. Cappo, C.J. Alexander, M.L. Good, Inorg.
Chem. 15 (1976) 2615;
M. Munakata, M. Maekawa, S. Kitagawa, M. Adachi, H. Masuda,
Inorg. Chim. Acta 167 (1990) 181;
B.G. Harvey, A.M. Arif, R.D. Ernst, Polyhedron 23 (2004) 2725;
J.M. Casas, B.E. Diosdado, L.R. Falvello, J. Fornies, A. Martin, A.J.
Rueda, Dalton Trans. (2004) 2733.
[8] T.A. Koizumi, T. Tomon, K. Tanaka, J. Organomet. Chem. 690
(2005) 4272.
[9] D. Gatteschi, C. Mealli, L. Sacconi, J. Am. Chem. Soc. 95 (1973)
2736;
L. Sacconi, C. Mealli, D. Gatteschi, Inorg. Chem. 13 (1974) 1985;
D. Gatteschi, C. Mealli, L. Sacconi, Inorg. Chem. 15 (1976) 2774;
C. Mealli, F. Zanobini, J. Chem. Soc. – Chem. Commun. (1982) 97;
A. Bencini, D. Gatteschi, L. Sacconi, Inorg. Chem. 17 (1978) 2670;
T. Tsuda, S. Ohba, M. Takahashi, M. Ito, Acta Crystallogr. C45
(1989) 887;
features an emission at
tetrahydrofuran.
kem = 604 nm in 2-methyl-
G. Blondin, J.J. Girerd, Chem. Rev. 90 (1990) 1359;
A. Bencini, E. Berti, A. Caneschi, D. Gatteschi, E. Giannasi, I.
Invernizzi, Chem. Eur. J. 8 (2002) 3660;
Acknowledgements
G. Tresoldi, S. Lo Schiavo, F. Nicolo, P. Cardiano, P. Piraino, Inorg.
Chim. Acta 344 (2003) 190;
This work was supported by the Bundesministerium fur
¨
Bildung und Forschung (BMBF) and the Austrian Grid.
I. Ara, J.M. Casas, J. Fornies, A.J. Rueda, Inorg. Chem. 35 (1996)
7345;
S.K. Patra, J.K. Bera, Organometallics 26 (2007) 2598.
[10] M. Maekawa, M. Munakata, S. Kitagawa, T. Kuroda-Sowa, Y.
Suenaga, M. Yamamoto, Inorg. Chim. Acta 271 (1998) 129.
[11] M. Basato, A. Biffis, G. Martinati, C. Tubaro, C. Graiff, T. Antonio,
A.A. Laura, A.M. Caporusso, J. Organomet. Chem. 691 (2006) 3464.
[12] G. Evens, P. Caluwe, Macromolecules 12 (1979) 803;
W. Tikkanen, W.C. Kaska, S. Moya, T. Layman, R. Kane, C.
Kruger, Inorg. Chim. Acta 76 (1983) L29;
Appendix A. Supplementary material
CCDC 654659 and 654654 contain the supplementary
crystallographic data for this paper. These data can be
obtained free of charge from The Cambridge Crystallo-
graphic Data Centre via www.ccdc.cam.ac.uk/data_re-
quest/cif. Supplementary data associated with this article
can be found, in the online version, at doi:10.1016/
j.inoche.2007.09.010.
M. Draux, I. Bernal, F. Lefoulon, R. Thummel, Inorg. Chim. Acta
104 (1985) 203;
W.R. Tikkanen, E. Binamirasoriaga, W.C. Kaska, P.C. Ford, Inorg.
Chem. 22 (1983) 1147;
A.T. Baker, W.R. Tikkanen, W.C. Kaska, P.C. Ford, Inorg. Chem.
23 (1984) 3254;
References
C. He, A.M. Barrios, D. Lee, J. Kuzelka, R.M. Davydov, S.J.
Lippard, J. Am. Chem. Soc. 122 (2000) 12683.
[13] T. Koizumi, K. Tanaka, Inorg. Chim. Acta 358 (2005) 1999;
R.P. Thummel, F. Lefoulon, S. Chirayil, Inorg. Chem. 26 (1987)
3072;
[1] D.G. Hendrick, T.E. Reed, Inorg. Chem. 8 (1969) 685;
D.G. Hendrick, Inorg. Chem. 8 (1969) 2328;
R.L. Bodner, D.G. Hendrick, J. Inorg. Nucl. Chem. 6 (1970) 421;
R.L. Bodner, D.G. Hendrick, Inorg. Chem. 9 (1970) 1255;
D.G. Hendrick, R.L. Bodner, Inorg. Chem. 9 (1970) 273;
R.J. Foster, R.L. Bodner, D.G. Hendrick, J. Inorg. Nucl. Chem. 34
(1972) 3795;
R.L. Bodner, D.G. Hendrick, Inorg. Chem. 12 (1973) 33;
D.G. Hendrick, R.J. Foster, Inorg. Chem. 12 (1973) 349;
K. Emerson, A. Emad, R.W. Brookes, R.L. Martin, Inorg. Chem. 12
(1973) 978;
W.R. Tikkanen, E. Binamirasoriaga, W.C. Kaska, P.C. Ford, Inorg.
Chem. 23 (1984) 141;
C. He, J.L. DuBois, B. Hedman, K.O. Hodgson, S.J. Lippard,
Angew. Chem. Int. Edit. 40 (2001) 1484.
[14] W.R. Tikkanen, C. Kruger, K.D. Bomben, W.L. Jolly, W.C. Kaska,
P.C. Ford, Inorg. Chem. 23 (1984) 3633.
[15] S.K. Patra, M. Majumdar, J.K. Bera, J. Organomet. Chem. 691
(2006) 4779.
[16] J.L. Zuo, W.F. Fu, C.M. Che, K.K. Cheung, Eur. J. Inorg. Chem.
(2003) 255;
A. Emad, K. Emerson, Inorg. Chem. 11 (1972) 2288.
[2] J.R. Wagner, D.G. Hendricker, J. Inorg. Nucl. Chem. 37 (1975) 1375.
[3] H. Schmidbaur, K.C. Dash, J. Am. Chem. Soc. 95 (1973) 4855;
K.R. Dixon, D.T. Eadie, S.R. Stobart, Inorg. Chem. 21 (1982)
4318;
T. Tanase, H. Takenaka, E. Goto, J. Organomet. Chem. 692 (2007)
175.

U. Monkowius et al. / Inorganic Chemistry Communications 10 (2007) 1473–1477
1477
[17] A. Juris, S. Campagna, V. Balzani, G. Gremaud, A. Vonzelewsky,
Inorg. Chem. 27 (1988) 3652.
[18] C.S. Campos-Fernandez, L.M. Thomson, J.R. Galan-Mascaros, O.Y.
Xiang, K.R. Dunbar, Inorg. Chem. 41 (2002) 1523;
C. He, S.J. Lippard, Inorg. Chem. 40 (2001) 1414.
[19] C. Bianchini, H.M. Lee, P. Barbaro, A. Meli, S. Moneti, F. Vizza,
New J. Chem. 23 (1999) 929.
[20] T. Tomon, T.A. Koizumi, K. Tanaka, Angew. Chem. Int. Edit. 44
(2005) 2229.
[21] H. Yersin (Ed.), Highly Efficient OLEDs with Phosphorecent
Material, Wiley-VCH, Weinheim, 2007;
the product. The suspension was filtered and recrystallized from
MeCN/Et2O yielding yellow crystals. Once precipitated the complex
is almost insoluble in DCM and CHCl3 and modestly soluble in hot
MeCN. Yield: 253 mg (0.29 mmol, 76%). 1H NMR (300 MHz,
CDCl3): d = 9.07 (br, 1H, C2/7-H), 8.51 (br, 1H, C4/5-H), 7.61 (dd,
C3/6-H), 7.24 – 7.44 (m, 20 H), 6.91 – 7.03 (m, 4 H) 6.69 – 6.74 (m,
2H); 13C{1H} NMR (75.5 MHz, CDCl3): d = 157.7 (dd,
JCP = 6.27 Hz C2/7), 137.4 (br, C4/5), 133.8 (s), 133.2 (dd,
JCP = 8.11 Hz), 131.6 (s), 131.0 (dd, JCP = 16.43 Hz), 129.8 (s),
128.4 (dd, JCP = 4.79 Hz), 124.4 (s, C3/6), 123.42 (dd,
JCP = 14.75 Hz), 119.8 (s); 31P{1H} NMR (121 MHz, CDCl3):
d = ꢀ 13.14 (s, DPEPhos), ꢀ143.16 (septet, JPF = 704 Hz, (PF6)ꢀ);
MS (ESI): m/z (%) = 601.1 [(DPEPhos)CuI]+ (53), 642.1 [(DPE-
Phos)CuI + MeCN]+ (100) 731.2 [(DPEPhos)Cu]+ (35); EA
[C44H34N2OP2Cu] PF6 calc.: C 60.25, H 3.91, N 3.19, found: C
60.36, H 3.97, N 3.18; UV/vis (MeCN): k(lge) = 380 (1.87), 301
(4.22), 224 nm (4.80); MF: [C44H34N2OP2Cu] PF6; MW = 877.19 g/
mol.
H. Yersin, Top. Curr. Chem. 241 (2004) 1.
[22] P.J. Giordano, M.S. Wrighton, J. Am. Chem. Soc. 101 (1979) 2888;
M. Wrighton, D.L. Morse, J. Am. Chem. Soc. 96 (1974) 998;
J.V. Caspar, B.P. Sullivan, T.J. Meyer, Inorg. Chem. 23 (1984) 2104.
[23] L. Yang, J.K. Feng, A.M. Ren, M. Zhang, Y.G. Ma, X.D. Liu, Eur.
J. Inorg. Chem. (2005) 1867.
[24] D.R. Striplin, G.A. Crosby, Coord. Chem. Rev. 211 (2001) 163.
[25] N. Armaroli, G. Accorsi, M. Holler, O. Moudam, J.F. Nierengarten,
Z. Zhou, R.T. Wegh, R. Welter, Adv. Mater. 18 (2006) 1313;
Q.S. Zhang, Q.G. Zhou, Y.X. Cheng, L.X. Wang, D.G. Ma, X.B.
Jing, F.S. Wang, Adv. Mater. 16 (2004) 432;
D.G. Cuttell, S.M. Kuang, P.E. Fanwick, D.R. McMillin, R.A.
Walton, J. Am. Chem. Soc. 124 (2002) 6.
[26] S.M. Kuang, D.G. Cuttell, D.R. McMillin, P.E. Fanwick, R.A.
Walton, Inorg. Chem. 41 (2002) 3313.
[27] C.E.A. Palmer, D.R. McMillin, Inorg. Chem. 26 (1987) 3837.
[28] C.E.A. Palmer, D.R. McMillin, C. Kirmaier, D. Holten, Inorg.
Chem. 26 (1987) 3167.
[29] F. Li, M. Zhang, G. Cheng, J. Feng, Y. Zhao, Y. Ma, S. Liu, J. Shen,
Appl. Phys. Lett. 84 (2004) 148.
[32] Crystal structure determination: Crystals of compounds 1 and 2 were
used for data collection on a STOE-IPDS diffractometer [36] with
˚
graphite monochromated Mo Ka radiation (k = 0.71073 A). The
structures were solved by direct methods (SIR-97) [37] and refined by
full-matrix least squares on F2 (SHELXL-97 [38]). The H atoms were
calculated geometrically and a riding model was applied during the
refinement process. Crystal data for 1: C11H6ClN2O3Re, M = 435.84,
ꢀ
translucent yellow prism, 0.19 · 0.15 · 0.10, triclinic, space group P1,
˚
˚
˚
a = 7.0534(8) A, b = 8.7475(10) A, c = 10.8185(13) A, a = 85.954ꢁ,
3
˚
b = 87.449(14)ꢁ, c = 70.873(13)ꢁ, V = 628.91(14) A , qcalc = 2.302 g
cmꢀ3, Z = 2, l = 9.873 mmꢀ1, T = 123 K, h range = 2.47 – 26.89ꢁ,
6884 reflections collected, 2486 [R(int) = 0.0234] unique reflections,
2438 observed reflections [I > 2r(I)], 163/0 parameters refined/
[30] Preparation of (nap)ReI(CO)3Cl, 1: The preparation was performed
according to a previously reported method with minor modifications
[2]. Re(CO)5Cl (150 mg, 0.41 mmol) and 1,8-naphthyridine (54 mg,
0.41 mmol) were dissolved in degassed toluene and heated to reflux
for 3 h. After cooling to room temperature, the yellow precipitate was
filtered and dried in vacuum. Yield: 173 mg (0.40 mmol, 97%). 1H
restraint, absorption correction: analytical from crystal shape, Tmin
,
ꢀ3
˚
Tmax = 0.3498, 0.1316, rfin (max/min) = 1.267/ꢀ0.966 e A
,
R1
[I P 2r(I)] = 0.0171, wR2 = 0.0443. Crystal data for 2: C44H34Cu-
N2OP2, F6P, M = 877.19, yellow prism, 0.22 · 0.16 · 0.10, mono-
˚
˚
clinic, space group P21/c, a = 11.0828(8) A, b = 28.827(2) A,
3
˚
˚
c = 12.6691(10) A, b = 103.440(9)ꢁ, V = 3936.7(5) A , qcalc = 1.480 g
cmꢀ3, Z = 4, l = 0.744 mmꢀ1, T = 123 K, h range = 1.89–25.78ꢁ,
49592 reflections collected, 7372 [R(int) = 0.0302] unique reflections,
6567 observed reflections [I > 2r(I)], 514/0 parameters refined/
NMR
(300 MHz,
CDCl3):
d = 9.09
(dd,
3JHH = 4.66,
4JHH = 1.65 Hz, 1H, C2/7-H), 8.53 (dd, 3JHH = 8.51, 4JHH = 1.65 Hz,
3
3
1H, C4/5-H), 7.79 (dd, JHH = 8.51, JHH = 4.66 Hz, 1H, C3/6-H);
13C{1H} NMR (75.5 MHz, CDCl3): d = 152.9 (s, C2/7), 137.3 (s, C4/
5), 125.5 (s, C3/6), quaternary Cs not detected; MS (EI): m/z
(%) = 130.0 [nap]+ (100), 351.9 [Mꢀ3CO]+ (3.3), 379.9 [Mꢀ2CO]+
(1.3), 407.9 [MꢀCO]+ (1.7), 435.9 [M]+ (1.3); MS (ESI): m/z
(%) = 130.9 [nap + H]+ (14), 442.0 [MꢀCl+MeCN]+ (100); UV/vis
(CHCl3): k(lge) = 415 (3.25), 313 (sh, 3.79), 301 (sh, 3.93), 276 nm
(4.18); EA [C11H6N2O3Re]Cl calc.: C 30.31, H 1.39, N 6.43, found: C
30.31, H 1.52, N 6.42; MF: C11H6N2O3ReCl; MW = 435.84 g/mol.
[31] Preparation of [(nap)CuI(DPEPhos)]PF6, 2: 1,8-naphthyridine (50 mg,
0.38 mmol), [CuI(NCMe)4]PF6 (143 mg, 0.38 mmol) and bis[2-
(diphenylphosphino)phenyl]ether (207 mg, 0.38 mmol) were dissolved
in degassed methylene chloride and heated to reflux for 3 h. The
solution was concentrated and diethyl ether was added to precipitate
restraint, absorption correction: analytical from crystal shape, Tmin
,
ꢀ3
˚
Tmax = 0.9576, 0.9033, rfin (max/min) = 0.523/ꢀ0.341 e A
,
R1
[I P 2r(I)] = 0.0309, wR2 = 0.0875.
[33] P. Wormell, A.R. Lacey, Chem. Phys. 118 (1987) 71.
[34] For computational details see Supplementary data.
[35] S.M. Kuang, P.E. Fanwick, R.A. Walton, Inorg. Chem. 41 (2002)
405.
[36] STOE IPDS-software, Version 2.89, STOE & CIE GmbH, Darms-
tadt, Germany, 1998.
[37] A. Altomare, G. Cascarano, C. Giacovazzo, A. Guagliardi, J. Appl.
Cryst. 1993 (26) (2002) 343.
[38] G.M. Sheldrick, SHELXL97. Program for Crystal Structure Refine-
ment, University of Go¨ttingen, Germany, 1997.