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Communication
NHC Ligands as Modulators of Luminescence in Three-
Coordinate Gold(I) Complexes with Spectacular Quantum Yields
Renso Visbal, Isaura Ospino, Jose Maria Lopez-De-Luzuriaga, Antonio Laguna, and M. Concepción Gimeno
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/ja401523x • Publication Date (Web): 13 Mar 2013
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Page 1 of 5 Journal of the American Chemical Society

1
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7 NHC Ligands as Modulators of Luminescence in Three-
8
9 Coordinate Gold(I) Complexes with Spectacular Quantum
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11
Yields
12
13 Renso Visbal,† Isaura Ospino,† José M. López-de-Luzuriaga,‡ Antonio Laguna,† and M. Con-
14 cepción Gimeno*,†
15
16
†
Departamento de Química Inorgánica-Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), CSIC-
17 Universidad de Zaragoza, 50009 Zaragoza, Spain.
18 ‡
Departamento de Química, Universidad de la Rioja, Centro de Investigación en Síntesis Química, Complejo Cien-
19 tífico Tecnológico, 26006 Logroño, Spain.
20 Supporting Information Placeholder
21 ABSTRACT: The first three-coordinate gold(I) NHC the geometry when interactions with other metals are
22 complexes have been prepared with the nido-carborane present.6
23 diphosphine. The complexes are brightly luminescent It is well known that many of the three-coordinate
24 and present very high quantum yield values. The carbene phosphine gold(I) complexes show luminescent proper-
25 ligand is able to modulate the energy of the emissions ties and these are mainly attributed to a metal centered
26 and depending upon the substituent the luminescence phosphorescence, in which the geometry changes in the
27 changes from blue to green. Theoretical calculations cor- excited state and arise from a Jahn-Teller distortion to-
28 roborate that the emissions are phosphorescence and ward a T-shape.7
29 arise from charge transfer (LML’CT) transitions from
nido-carborane ligand (L) to metal/ligand group We have previously reported that complexes of the
30 form [AuCl(PR3)] react with different carborane diphos-
31 ‘gold(I)−NHC ligand’ (ML’).
phines to afford the corresponding three-coordinate
32 The chemistry of the synthesis, characterization and gold(I) complexes [Au{(PR)2C2B9H10}(PR'3)],8 and we
33 application of new N–Heterocyclic Carbene (NHC) tran- believe that under the same reaction conditions it is pos-
34 sition metal complexes has undergone rapid develop- sible to obtain analogous (NHC) gold diphosphine com-
35 ment in the past few years.1 In particular gold NHC com- plexes. Herein, we report the synthesis, optical proper-
36 plexes have attracted a great deal of interest because the ties, and the structural and theoretical characterization
37 numerous applications in catalysis, medicine and mate- of the first neutral three-coordinate NHC gold(I) com-
38 rials chemistry.2 An important property shown by these plexes (scheme 1). We have chosen several NHC ligands
39 gold NHC species is their luminescence. Several com- with differences in their electronic and steric properties
plexes have been described in which the emissive nature in order to explore how this can affect the stability of the
40
of the compounds is due to the presence of metallophilic three–coordinate species (Chart 1). Furthermore, these
41
interactions, the π delocalized nature of the substituents factors together with or without the use of auxiliary
42 in the imidazole ring or the coordination to a chromo-
43 chromophore groups as substituents will allow for the
phore ligand.3 modulation of their luminescent properties. We have
44
The great coordination capacity of NHCs towards tran- achieved that this selection of carbene ligands is key in
45
sition metals has allowed many complexes to be obtained both the energy of the emissions and in the high quan-
46 which contain, in addition to the NHC ligand, different tum yields observed for these complexes.
47 organic and inorganic functions coordinated to the met-
48 Chart 1. NHC ligands used.
al, such as halogens, pseudohalogens, pyridines, or even
49 labile molecules.4 Surprisingly, there are few examples of
50 (NHC) gold(I) phosphine complexes reported in the lit-
51 erature, although both ligands form very strong bonds to
52 the gold center, and the first [NHC−Au−PR3]+ adduct was
53 reported by Grützmacher et al in 2002. Until now only a
The reaction of the corresponding [AuCl(NHC)] com-
54 few cationic NHC gold(I) phosphine complexes have plex with the carborane diphosphine [(PPh2)2C2B10H10]
55 been reported, all of which contain one phosphorus atom gives, after 30 minutes under reflux, complexes (1–7) in
56 bonded directly to the metal center and in all cases the
good yield and purity by filtration and after washing with
57 coordination around the metal center is of a linear na-
ethanol.
58 ture.5 Gold(I) center shows a clear preference for a linear
59 geometry, and to the best of our knowledge all the NHC
60 compounds reported have a linear environment around
the metal, and only in some cases there is a distortion of
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Scheme 1. Synthesis of the three–coordinate NHC the order of the tendency to linearity can be established
1 gold(I) complexes. as 5>1>4, and must be attributed to the presence of
2 asymmetric substituted carbene ligand in complex 5 or
3 to the bulkiness of the substituents in the carbene ligand
4 in complexes 1and 4.
5 All complexes show a singlet around 50 ppm in the
6 31P–{1H} NMR spectra and were found more upfield than

7 the analogous complex with only phosphines (around 63

8 Single crystals suitable for X–Ray diffraction analysis ppm).8b The 1H NMR spectra for complexes 1–7 show, in
9 were obtained for 1, 4 and 5. The molecular structure of addition to the signals characteristic for the bisisopro-
10 1 is depicted in figure 1. The geometry around the gold(I) pyl(phenyl), mesityl and acridine derivatives, broad sig-
11 center is distorted trigonal planar, with bond angles nals at around 0.5 and –2 ppm corresponding to the B−H
12 C1−Au1−P1 and C1−Au1−P2 of 130.40(6)° and bond and to the hydride of the nido–carborane, respec-
13 148.34(6)°, respectively. As we have observed for other tively. The best evidence of the stability of these com-
14 three-coordinate gold(I) complexes containing carborane plexes in solution has been found in the 13C–{1H} NMR
15 diphosphines, 1 has a small P1−Au1−P2 (81.223(19)°) spectra, in which the signal corresponding to the car-
16 bite angle, which is attributed to the great rigidity of the benic carbon appears as a triplet with a C−P coupling
17 carborane.9 The interplanar angle between the carbenic constant around 50 Hz. Substantial differences between
18 ring and the trigonal plane around the metal center is these complexes are found in the 13C–{1H} NMR spectra
48°, and this disposition of the carbene ligand in 1 could that show triplets between 185-188 ppm for the unsatu-
19
be the result of steric hindrance between the isopropyl– rated NHC ligands including acridine, IPr and IMes sub-
20
phenyl and phenyl groups. Although the Au1−C1 stituents, while for the complexes with the saturated
21 NHC ligands the corresponding signals are significantly
22 (2.051(2) Å) and Au1−P2 (2.3681(6) Å) bond distances
deshielded appearing around 214 ppm.
23 found are in good agreement with Au−C and Au−P bond
distances previously reported for NHC−M−PR3 complex- Although all of the starting materials for the acridine
24
derivatives ([AuCl(NHC)]) are emissive,9 none of the
25 es,5 the other Au1−P1 bond distance of 2.5311(5) Å is
three-coordinate gold(I) complexes 5–7 show lumines-
26 quite different.
cence. However, complexes 1–4 are strongly luminescent
27 showing emissions in the blue-green region despite not
28 having a chromophore group (see photophysical data in
29 table 1). The absorption spectra of complexes 1–4 are
30 featureless showing a single absorption band at around
31 300-310 nm which is tentatively associated to IL transi-
32 tions. Complexes 1–4 display a modulation of the lumi-
33 nescence upon excitation at 370 nm showing emission
34 bands from 470 nm for SIMes (4) to 520 nm for SIPr (2)
35 derivatives in the solid state (see figure 2).
36
37
38 Figure 1. a. Ortep diagram for 1 with 50 % probability el-
39 lipsoids. Hydrogen atoms are omitted for clarity. b. View of
the three-coordination around the gold(I) center.
40
41 Complex 4 shows an almost perpendicular disposition
42 between the carbenic ring and the trigonal plane around
43 the metal center (82°) in solid state (see the supporting
44 information), and this geometry could be favored by the
45 planarity of the mesityl groups which lie in the middle of
46 the phenyl groups. In this case, the smallest difference
47 found for the Au−P bond distances (0.03 Å) compared to
48 the found for 1 (0.16 Å), could suggest a better overlap of
the involved bonding orbitals. In fact, this three- Figure 2. Normalized emission spectra of complexes 1–4 in
49
coordinate geometry is less distorted than that of 1, since the solid state upon excitation (370 nm) at 298 K.
50
the C1−Au1−P1 and C1−Au1−P2 angles were 132.86(12)°
51
and 140.31(12)°, respectively. The acridine derivative 5 No substantial changes were observed for the emis-
52 has a three-coordinate geometry much more distorted sions at 77 K in the solid state, but a slight red shift aris-
53 since the C1−Au1−P1 and C1−Au1−P2 angles were ing from a thermal contraction that reduces the intera-
54 121.9(2)° and 155.6(2)°, respectively (see the supporting tomic distances and, consequently, the band gap energy.
55 information). All these structures have a distorted trigo- Also, a moderate bathochromic shift was observed in
56 nal planar geometry. The distortion mainly arises at the degassed CH2Cl2 at room temperature, compared to the
57 small bite angle of the diphosphine, which is very similar solid state, which is due to an increase of the polarity of
58 for the three complexes. According to the C−Au−P angles the molecules in the excited state, which gives rise to a
59 lowered relaxed state in a polar solvent. This effect sug-
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gests a photoinduced charge transfer as origin of the ob- the dσ of gold(I) with its NHC ligand. The presence of the
1 served luminescence.10 The life–times found in both solid dxy orbital in the HOMO, with higher energy that the cor-
2 state and in solution (10.9-21.8 µs) suggest that the elec- responding dz2 in a linear environment explain the low-
3 tronic transitions involved in the blue-green emissions est energy needed to reach triplet excited state.
4 are of phosphorescent nature and this is in agreement
5 with previously results found for other three-coordinate
6 complexes.11 Significantly, the four complexes show very
7 high quantum yield values, reaching almost 100% for
8 complex 2. This quantum yield value is exceptional and
9 only two NHC complexes, of platinum and gold, have
10 values around 90%.1d,3g Therefore, this characteristic to-
gether with the lifetimes in the microsecond range and
11
the colors of the emissions in the blue-green region,
12 make these species very attractive for future studies in-
13 cluding practical applications as OLED emitters.
14
Table 1. Luminescence data for complexes 1-4
15
16 Emissio-
Complex
na
17 Figure 3. Contour plots of the frontier molecular orbit-
Medium (T [K]) λmax [nm] τo [µs]d Φem [%]d
18 als for complex 1, 4 and 5.
1 solid (298, 77) 500, 500 16.2 34
19
20 CH2Cl2 (298, 77) 520b, 490 10.9 Taking into account the TDDFT calculations together
21 2 solid (298, 77) 520, 530 21.8 99 with the modulation of the luminescence observed by the
22 CH2Cl2 (298, 77) 545, 495 11.6 use of different NHC ligands, we can propose the as-
23 3 solid (298, 77) 490, 495 13.4 45 signment of the origin of the phosphorescent emission as
24 CH2Cl2 (298, 77) 540b, 500 12.2 derived from the nido-carborane ligand to metal/ligand
25 4 solid (298, 77) 470, 480 15.8 65
group ‘gold(I)−NHC ligand’ (ML’) charge transfer
26 (LML’CT) transition.
CH2Cl2 (298, 77) 570c, 490 11.4
27 aEmission band upon excitation at 370 nm. bEmission
We can propose that the non-emissive behavior in the
28 complexes 5–7 which have the highly electron-rich acri-
band upon excitation at 330 nm. cEmission band upon
29 dine group is probably because the LUMO of 5 is pre-
excitation at 350 nm. dLifetime and luminescence quan-
dominantly acridine-based with little contribution from
30 tum yield, measured at room temperature.
the carbene ligand and with no contribution from metal.
31 In order to confirm the origin of the emissions we have As we saw earlier, the orbitals involved in the sin-
32 performed theoretical calculations. For this we first stud- glet→triplet transition for complexes 1 and 4 are HOMO
33 ied the electronic structures of the complexes 1 and 4 and LUMO, and the second one is predominantly metal-
34 obtained through single-point DFT calculations using based with contributions from phosphine and carbene
35 geometric parameters from XRD analysis (figure 3). Lat- ligands, and these differences could be the reason for the
36 er, we carried out TDDFT calculations of the excitation quenching of the photoluminescence in complexes 5–7.
37 singlet→triplet, because the emission lifetimes in the
In attempts to modify the optical properties of these
38 microsecond range, together with the observed large
novel complexes, we used NHC ligands with different
39 Stokes shift, suggest that the emission is of triplet par-
steric and electronic properties to those of the NHC lig-
40 entage. A visual inspection of the frontier orbitals of both
ands in complexes 1–7. Unexpectedly, the use of the iso-
41 complexes 1 and 4 shows that the highest occupied mo-
lecular orbitals (HOMO) is mainly composed of the delo- propyl or 2–pyridine N–substituted carbenes gave a solid
42 that was identify as the four–coordinate species
calized orbitals on the nido-carborane ligand (L) and in
43 [Au{(PPh2)2C2B9H10}{(PPh2)2C2B10H10}] (III) (scheme 2).
the gold−C(NHC) bond. The lowest occupied molecular
44
orbitals (LUMO) is predominantly located at the gold(I) The presence of an AA′BB′ system in the 31P–{1H} NMR
45 center with further contributions from the C (NHC) and spectrum in CDCl3 at around 42 and 38 ppm confirms
46 P atoms. This analysis shows also that in general the this hypothesis.12 In order to better understand the for-
47 HOMOs are mainly located at the nido-carborane ligand mation mechanism of III we carried out the reaction in
48 CDCl3 to avoid the nucleophilic attack from EtOH. After
with a strong contribution of the gold−C(NHC) bond,
49 and the LUMOs are mainly located at the phosphine and addition of NHC−Au−Cl derivative to the carborane di-
50 NHC ligands, and the metal center (see the supporting phosphine ligand, the signal corresponding to the free
51 information). phosphine (7 ppm) disappears and a new singlet at
52 around 42 ppm in the 31P–{1H} nmr spectrum character-
The TDDFT calculations show that the orbitals in- istic of the cationic four-coordinate complex II appears,13
53 volved in the singlet→triplet transition are HOMO and whilst in the 1H NMR spectrum the resonances attributed
54 LUMO with energy of 2.8835 eV (429.98 nm) for com- to the bis-carbene I are present.14 This fact confirms that
55 plex 1 and HOMO and LUMO with energy of 2.9765 eV the bulkiness of the NHC ligand is key in the formation
56 (417.54 nm) for complex 4. The simplest analysis of this and stabilization of the three-coordinate gold(I) com-
57 excitation shows that the HOMO involved is a π-bonding plexes.
58 orbital between the nido-carborane ligand, pπ, and
gold(I)-dπ. The LUMO is an antibonding combination of Scheme 2. Formation mechanism of III.
59
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R
Ph 2P
R Rev. 2009, 109, 3561. (b) Marion, N.; Nolan, S. P.
1 N C N Ph2
P
Chem. Soc. Rev., 2008, 37, 1776. (c) Hickey, J. L.;
C
2 Au Cl + Ph 2P Au C Cl Ruhayel, R. A.; Barnard, P. J.; Baker, M. V.; Berners-
C
N N P
Price, S. J.; Filipovska, A. J. Am. Chem. Soc. 2008,
3 Ph2
R R 130, 12570. (d) Hashmi, A. S. K.; Riedel, D.; Rudolph,
4 R = isopropyl, 2-pyridine Intermediate
M.; Rominger, F.; Oeser, T. Chem. Eur. J. 2012, 18,
Exchange
5 3827. (e) Powell, A. B.; Bielawski, C. W.; Cowley, A. H.
R R Ph 2
6 P
Ph2
P
J. Am. Chem. Soc. 2009, 131, 18232.
N N
7 Au Cl +
C
Au C Cl
(3) (a) Au, V. K.-M.; Wong, K. M.-C.; Zhu, N.; Yam, V. W.-
C
P P C
W. J. Am. Chem. Soc. 2009, 131, 9076. (b) Strasser, C.
8 N N Ph 2 Ph 2
R
E.; Catalano, V. J. J. Am. Chem. Soc. 2010, 132, 10009.
9 R I II
(c) Chow, A. L.-F.; So, M.-H.; Lu, W.; Zhu, N.; Che, C.-
10 Degradation
M. Chem. Asian J. 2011, 6, 544. (d) Catalano, V. J.;
11 Ph 2
Ph2
Moore, A. L.; Shearer, J.; Kim, J. Inorg. Chem. 2009,
12 C
P
Au
P H 48, 11362. (e) Fortman, G. C.; Poater, A.; Levell, J. W.;
P
C
C Gaillard, S.; Slawin, A. M. Z.; Samuel, I. D. W.; Cavallo,
13 C P
Ph 2 Ph2
L.; Nolan, S. P. Dalton Trans. 2010, 39, 10382. (f) Par-
14 III tyka, D. V.; Esswein, A. J.; Zeller, M.; Hunter, A. D.;
15 Gray, T. G. Organometallics 2007, 26, 3279. (g) Bar-
In conclusion, we have synthesized and characterized on, M.; Tubaro, C.; Biffis, A.; Basato,M.; Graiff, C.;
16
the first three-coordinate NHC gold(I) complexes, which Poater, A.; Cavallo, L.; Armaroli, N.; Accorsi, G. Inorg.
17
are very stable in both solid state and solution. As we Chem. 2012, 51, 1778.
18 expected, most of these complexes are highly lumines- (4) (a) Tsui, E. Y.; Müller, P.; Sadighi, J. P. Angew. Chem.
19 cent with emission energies from blue to green and the Int. Ed. 2008, 47, 8937. (b) Gaillard, S.; Slawin, A. M.
20 complexes present spectacular quantum yields. Surpris- Z.; Nolan, S. P. Chem. Commun. 2010, 46, 2742. (c)
21 ingly, the presence of a chromophore group like acridine, Brown, T. J.; Dickens, M. G.; Widenhoefer, R. A. J. Am.
22 led to the quenching of photoluminescence. The use of Chem. Soc. 2009, 131, 6350. (d) de Frémont, P.; Mari-
on, N.; Nolan, S. P. J. Organomet. Chem. 2009, 694,
23 no very bulky NHC ligands with different electronic
551. (e) Laitar, D. S.; Müller, P.; Gray, T. G.; Sadighi, J.
24 properties affording the homoleptic species I and II, and P. Organometallics 2005, 24, 4503.
25 subsequent degradation to afford III, confirms that the (5) (a) Boöhler, C.; Stein, D.; Donati, N.; Grützmacher, H.
26 bulkiness of the NHC ligands is essential for the for- New J. Chem., 2002, 26, 1291. (b) Baker, M. V.; Bar-
27 mation of these three-coordinate gold(I) complexes. nard, P. J.; Berners-Price, S. J.; Brayshaw, S. K.; Hick-
28 ey, J. L.; Skelton, B. W.; White, A. H. J. Organomet.
Chem. 2005, 690, 5625. (c) Gaillard, S.; Nun, P.;
29 ASSOCIATED CONTENT Slawin, A. M. Z.; Nolan, S. P. Organometallics 2010,
30 Supporting Information. Experimental details, synthe- 29, 5402. (d) Radloff, C.; Weigand, J. J.; Hahn, F. E.
31 sis, characterization, and crystallographic data (CIF) for 1, 4 Dalton Trans., 2009, 9392. (e) Townsend, N. S.;
32 and 5. Excitation and emission spectra of complexes 1-4, Green, M.; Russell, C. A. Organometallics 2012, 31,
33 and details of the computational studies. This material is 2543.
available free of charge via the Internet at (6) Braunschweig, H.; Brenner, P.; Dewhurst, R. D.;
34 Kaupp, M.; Müller, R.; Östreicher, S. Angew. Chem.
http://pubs.acs.org.
35 Int. Ed. 2009, 48, 9735.
36 AUTHOR INFORMATION (7) (a) Barakat, K. A.; Cundary, T. R.; Omary, M. A. J. Am.
37 Chem. Soc. 2003, 125, 14228. (b) Sinha, P; Wilson, A.
38 Corresponding Author K.; Omary, M. A. J. Am. Chem. Soc. 2005, 127, 12488.
39 *gimeno@unizar.es. (8) (a) Crespo, O.; Gimeno, M. C.; Jones, P. G.; Laguna, A.;
40 López-de-Luzuriaga, J. M.; Monge, M.; Pérez, J. L.;
Notes Ramón, M. A. Inorg. Chem. 2003, 42, 2061. (b) Cres-
41 The authors declare no competing financial interest. po, O.; Gimeno, M. C.; Jones, P. G.; Laguna, A. Inorg.
42 Chem. 1996, 35, 1361.
43 ACKNOWLEDGMENT (9) Gimeno, M. C.; Laguna, A.; Visbal, R. Organometallics
44 Authors thank the Ministerio de Economía y Competitivid- 2012, 31, 7146.
45 ad-FEDER (CTQ2010-20500), DGA-FSE (E77) for financial (10) Valeur, B. in Molecular Fluorescence. Principles and
46 support and to the Supercomputing Centre of Galicia Applications, Wiley-VCH, Weinheim, 2002, p. 200-
47 (CESGA-CSIC). 224.
48 (11) Czerwieniec, R.; Hofbeck, T.; Crespo, O.; Laguna, A.;
49 REFERENCES Gimeno, M. C.; Yersin, H. Inorg. Chem. 2010, 49,
50 (1) (a) Samojłowicz, C.; Bieniek, M.; Grela, K. Chem. Rev. 3764.
51 2009, 109, 3708. (b) Dobereiner, G. E.; Nova, A.; (12) Crespo, O.; Gimeno, M. C.; Jones, P. G.; Laguna, A.; Vi-
52 Schley, N. D.; Hazari, N.; Miller, S. J.; Eisenstein, O.; llacampa, M. D. Angew. Chem. Int. Ed. Engl. 1997, 36,
Crabtree, R. H. J. Am. Chem. Soc. 2011, 133, 7547. (c) 993.
53 Liu, W.; Gust, R. Chem. Soc. Rev. 2013, 42, 755. (d)
54 (13) Crespo, O.; Gimeno, M. C.; Laguna, A.; Jones, P. G. J.
Unger, I.; Meyer, D.; Molt, O.; Schildknecht, C.; Chem. Soc. Dalton Trans. 1992, 1601.
55 Münster, I.; Wagenblast, G.; Strassner, T. Angew.
Chem. Int. Ed. 2010, 49, 10214. (14) Baker, M. V.; Barnard, P. J.; Berners-Price, S. J.; Bray-
56 shaw, S. K.; Hickey, J. L.; Skelton, B. W.; White, A. H.
57 (2) (a) Lin, J. C. Y.; Huang, R. T. W.; Lee, C. S.;
Bhattacharyya, A.; Hwang, W. S.; Lin, I. J. B. Chem. Dalton Trans. 2006, 3708.
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