Journal of Molecular Liquids 194 (2014) 188192

Contents lists available at ScienceDirect

Journal of Molecular Liquids

journal homepage: www.elsevier.com/locate/molliq

Oxidative uorescence quenching of Mg-phthalocyanine by quinones

M. Asha Jhonsi a,, A. Kathiravan b
a b

Department of Chemistry, B.S. Abdur Rahman University, Chennai, Tamil Nadu 600 048, India National Centre for Ultrafast Processes, University of Madras, Taramani Campus, Chennai, Tamil Nadu 600 113, India

a r t i c l e

i n f o

a b s t r a c t
The quenching of the excited singlet state of magnesium phthalocyanine (MgPc) by quinones was investigated in DMSO, acetonitrile and methanol. The quinones used were benzoquinone (BQ), duroquinone (DQ) and naphthaquinone (NQ). Fluorescence intensity/lifetime decreases with increasing concentration of the quinone following a linear SternVolmer behavior. Bimolecular quenching rate constants (kq) obtained from both the steady-state and time-resolved measurements for the singlet state quenching process were agreed well. Singlet quenching rate constants are diffusion controlled in all solvents. The quenching rate constants were decreased when the polarity of solvent is decreased. The thermodynamic parameter (Get) estimated by using the RehmWeller equation were used to propose a suitable mechanism for electron transfer occurring between MgPc and quinones. The obtained Get is more negative which clearly indicates that electron transfer type of mechanism is operative in these systems. 2014 Elsevier B.V. All rights reserved.

Article history: Received 24 August 2013 Received in revised form 17 February 2014 Accepted 25 February 2014 Available online 14 March 2014 Keywords: Phthalocyanine Quinone Fluorescence quenching TCSPC PET

1. Introduction Electron transfer (ET) reaction involves the transfer of an electron from a donor to an acceptor which can occur both thermally and photochemically. The latter reaction is referred to as photoinduced electron transfer (PET) [1]. The development of bioinspired electron donor acceptor complexes that can undergo efcient PET is attracting more in the current scenario. These systems mimic the function of photosynthetic reaction center and are useful for solar energy conversion, storage and in many optoelectronic devices [2,3]. Moreover, the investigation of PET is essential to understanding the physical processes involving in dye sensitized solar cells (DSSC). In a DSSC [4], dyes are used to absorb incident light, which leads to electron injection from the excited state dye to the conduction band of semiconductor electrode, normally titanium dioxide (TiO2). In such a system, the dye serves as an electron donor and a semiconductor is used as electron acceptor. A number of dyes [5] have been studied in an attempt to nd correlation between the molecular structure of the dye and its ability to generate a photocurrent in a DSSC. In this context, ruthenium complexes represent an extremely popular for investigations of photoinduced electron transfer [6,7] because the ruthenium complex sensitizers (N3, N719 and black dye) have shown high photoelectric conversion efciencies of over 12% under AM 1.5 conditions [811]. On the other hand, porphyrins are also one of the choices for DSSC due to their close resemblance to the photosynthetic pigment and chlorophyll and their extremely high
Corresponding author. E-mail address: asha@bsauniv.ac.in (M. Asha Jhonsi).

molar extinction coefcient (i.e., intense Soret band at 400 nm and moderate Q bands at 500600 nm) and synthetic versatility. Recently, Yella et al. have raised the power conversion efciency of a porphyrinbased DSSC beyond 12% by using a cobalt-based electrolyte [12]. To date, various organic dyes including coumarin, indoline, squaraine, polyene, cyanine, hemicyanine, oligothiophene, perylene, carbazole, benzothidizole and truexene have been developed and have attained high efciencies up to 10.3% [5,13]. Among the red-light-absorbing dyes, metallophthalocyanine (MPc) is one of the most promising because of its high hardiness and intense absorption band (called the Q-band) at 650700 nm [14,15]. While various MPcs have been synthesized and evaluated as light-harvesting dyes for DSSCs, the conversion efciencies of MPc-based DSSCs have been lower than those of other macrocyclic dyes with similar absorption spectra, such as porphyrins [1618]. The highest power conversion efciency of DSSC sensitized by an MPc is 4.6% [19]. Recently, Kimura et al. [20] reported an improved power conversion efciency of MPc is 5.3% by enhancing the pushing ability of the peripheral bulky substituents through the introduction of electron-donating methoxy groups. Measuring the ET kinetics between the sensitizer and inorganic semiconductor has been a subject of intense research because understanding the interfacial injection process is essential for designing the interfaces that are favorable for charge injection and high solar cell efciency. Hence, understanding photophysical processes in MPc is therefore becoming an interesting topic [21]. In order to imitate the ET process operating between excited dyes and a semiconducting electrode in a DSSC, one can monitor the correlation between the dye uorescence quenching behaviors together with electron acceptor

http://dx.doi.org/10.1016/j.molliq.2014.02.033 0167-7322/ 2014 Elsevier B.V. All rights reserved.

M. Asha Jhonsi, A. Kathiravan / Journal of Molecular Liquids 194 (2014) 188192

189

using uorescence spectroscopy. In other words, the photophysical characterization of the electron donor and electron acceptor in a homogenous system is a requirement for the better understanding of the effects occurring in DSSC. Recently, Yenilmez et al. [22] reported the uorescence quenching of zinc phthalocyanine (ZnPc) with benzoquinone (BQ). They observed that there is a progressive decrease in uorescence intensity of ZnPc as the concentration of BQ increases. The observed quenching is due to electron transfer with rate constant of 9.7 109 M 1 s 1, which was one magnitude lower than when compared to unsubstituted ZnPc (5.59 1010 M 1 s 1) due to presence of thiazole groups. However, the BQ quenching of simple ethoxy group substituted ZnPc shows almost identical quenching rate constant comparing with standard ZnPc [23]. On the other hand, improved BQ quenching rate constant (1011 M 1 s 1) was observed with a Schiff base-connected ZnPc [24]. The general idea of this paper is to follow the optical properties of the MPc in the presence of acceptor in a homogeneous medium, in order to elucidate the electron-transfer reaction operating between phthalocyanine and a strong electron acceptor. For that we have chosen quinone derivatives as an accepting material due to their essential role in electron transport in natural systems [25,26]. In this context, the uorescence quenching and electron transfer process in a solution of MgPc in the presence of quinone were studied. We have used both the steady-state (SS) and time-resolved (TR) uorescence techniques to monitor the electron transfer processes occur between excited MgPc and quinones. Chemical structures of MgPc and quinones are shown in Scheme 1.

0.8

0.6

Absorbance

0.4

No DQ 5mM DQ

0.2

0.0 500

550

600

650

700

750

800

Wavelength (nm)
Fig. 1. UV-visible absorption spectrum of MgPc in the absence (solid line) and presence (dashed line) of duroquinone (5 10 3 M) in acetonitrile. (For interpretation of the references to colour in this gure, the reader is referred to the web version of this article.)

3. Results and discussion 3.1. Ground state absorption characteristics Fig. 1 shows the ground state absorption spectra of MgPc in the absence and presence of duroquinone in acetonitrile. In the absence of duroquinone, MgPc exhibits sharp and intense absorption in its Q band region. However, we observed that there is no change in the absorption spectrum of MgPc in the presence of highest concentration of duroquinone (5 mM), and also, there is no peak shift and nor new peak was formed. This inference indicates the absence of interaction between MgPc and duroquinone in the ground state. The other two quinones such as nathaquinone and benzoquinone were also shown the similar type of interaction; their spectra were not shown here. 3.2. Steady-state uorescence characteristics

2. Experimental 2.1. Materials Magnesium phthalocyanine (MgPc) was purchased from Aldrich and used as such without further purication. All the quinones were obtained from Fluka.

2.2. Instrumentation 2.2.1. Spectroscopic measurements Absorption spectra were recorded using Cary 300 UV-visible spectrophotometer. The steady-state uorescence quenching measurements were carried out with JASCO FP-6500 spectrouorometer. For uorescence studies, much diluted solutions were used to avoid spectral distortions due to the inner-lter effect and emission reabsorption. Time-resolved uorescence decays were obtained by the time correlated single-photon counting (TCSPC) technique exciting the sample at 400 nm. The typical full width at half-maximum (FWHM) of the system response using a scatterer is about 50 ps. Data analysis was carried out by the software provided by IBH (DAS-6), which is based on deconvolution techniques using nonlinear least-squares method and the quality of the t is ascertained with the value of 2 b 1.2.

Fig. 2 shows the uorescence emission spectrum of MgPc in the absence and presence of various concentrations of naphthaquinone in acetonitrile. Result from the Fig. 2 indicates that there is a regular decrease in the emission intensity of MgPc with the addition of naphthaquinone. This shows the quenching has been occurred between MgPc and quinone. At the same time, there is no signicant peak shift and no peak broadening was observed. The other two quinones (benzoquinone and duroquinone) were also gave the similar type of quenching behavior (spectra were not shown here). In order to predict the possible quenching mechanism, the uorescence quenching data were subjected to SternVolmer analysis [27] using SternVolmer Eq. (1) as follows: I0 =I 1 K SV Q
ss

O
N N N N N

Mg
N

Magnesium Phthalocyanine

Duroquinone

Benzoquinone 1,4 Naphthaquinone

Scheme 1. Structure of MgPc and quinines.

190

M. Asha Jhonsi, A. Kathiravan / Journal of Molecular Liquids 194 (2014) 188192

400

Table 1 Bimolecular quenching rate constant (kq) for MgPc in various solvents from steady-state measurements.

300

Intensity

200

No NQ 1 mM NQ 2 mM NQ 3 mM NQ 4 mM NQ 5 mM NQ

S. No

Quinones

kq / (1010 M1 s1) DMSO CH3CN 1.66 1.43 1.10 CH3OH 1.24 1.16 1.06

1 2 3

Naphthaquinone Benzoquinone Duroquinone

4.43 4.11 3.75

100

with the reported values [28]. Meaning that this commercial MgPc shows similar kind of donating property in the excited state by comparing reported ZnPc derivatives.
630 660 690 720 750

3.3. Time-resolved uorescence characteristics The steady-state measurement alone is not enough to conrm the type of uorescence quenching whether it is dynamic or static in nature. In general, lifetime measurement is the most denitive method to distinguish the static and dynamic quenching process. Fig. 4 shows the uorescence decay of MgPc in the absence and presence of different concentrations of benzoquinone in acetonitrile solvent. The emission of MgPc exhibits single exponential decay not only in the dilute solution but also in the presence of benzoquinone. While increasing the concentration of benzoquinone, a gradual decrease in the uorescence lifetime of MgPc has been observed. The result from the lifetime measurement con rms that the quenching of MgPc by quinone is belongs to dynamic type. The other two quinones such as nathaquinone and duroquinone also show the similar type of decrease in uorescence lifetime of MgPc, their spectra were not shown here. The bimolecular quenching rate constant has also been calculated from the time-resolved uorescence quenching measurements using the following Eq. (3): 0 = 1 K SV Q 1 kq 0 Q
TR TR

Wavelength (nm)
Fig. 2. Steady-state uorescence quenching of MgPc (1 10 M) in the presence of various concentrations of naphthaquinone (05 103 M) in acetonitrile. (For interpretation of the references to colour in this gure, the reader is referred to the web version of this article.)
5

where I0 and I are the uorescence intensities of the uorophore (MgPc) in the absence and the presence of quencher (quinones), respectively, Ksv is the SternVolmer quenching constant and [Q] is the concentration of quencher (quinones). The bimolecular quenching rate constant (kq) is calculated using Eq. (2) as follows: K sv 0 kq 2

where 0 is the excited state lifetime of MgPc in the absence of quinone, obtained from the uorescence lifetime measurement (6.6 ns). Plots of I0/I vs [Q] were linear for all three quinone with MgPc systems, indicating that dynamic nature of quenching process has been occurred. The comparison of SternVolmer plot for the quenching of MgPc by the three quinones in acetonitrile was shown in Fig. 3. Such observations on dynamic quenching based on steady-state method are quite common. From the slope of linear S-V plot, we determined the KSV, and using Eq. (2), we obtained the kq values, which are shown in Tables 1 and 2. It was proposed that the decreased uorescence of ZnPc with benzoquinone was due to an electron-transfer reaction [24]. Moreover, the obtained quenching rate constants were in excellent agreement

The symbols 0 and are the lifetime of uorophore, in the absence and presence of quencher. The typical comparison of SternVolmer plots for the time-resolved uorescence quenching of MgPc by quinones in acetonitrile medium is shown in Fig. 5. The plots were linear with the correlation coefcient (R2) of greater than 0.9969, indicating

1.6 1.5 1.4 1.3 1.2 1.1 1.0

104

I0/I

Log Counts

NQ BQ DQ

103

IRF No BQ 1 mM BQ 2 mM BQ 3 mM BQ 4 mM BQ 5 mM BQ

102

101

100 0 1 2 3 4 5 10 20 30 40 50

[Q] x 10-3 M
Fig. 3. Comparison of SternVolmer plot for the steady-state uorescence quenching of MgPc (1 10 5 M) by quinones in various concentrations (05 103 M) in acetonitrile. (For interpretation of the references to colour in this gure, the reader is referred to the web version of this article.)

Time (ns)
Fig. 4. Time-resolved uorescence quenching of MgPc (1 105 M) in the presence of various concentrations of benzoquinone (05 103 M) in acetonitrile. (For interpretation of the references to colour in this gure, the reader is referred to the web version of this article.)

M. Asha Jhonsi, A. Kathiravan / Journal of Molecular Liquids 194 (2014) 188192

191

1.5

1.4

1.3

0/

1.2

1.1

1.0 0 1 2 3 4 5

test the formation of exciplex, we have measured the kq values by varying solvent polarity. The kq values decreased from more polar solvent to less polar solvent. The inverted solvent effect has not been observed in this case. From this observation, the formation of an exciplex can be ruled out. The mechanism of energy transfer from the excited MgPc to quinones is also ruled out due to absence of overlap between the emission and absorption spectra of MgPc and duroquinone (Fig. 6). A mechanism involving hydrogen atom transfer can be excluded because of exergonic thermodynamics calculated from the RehmWeller equation (discussed in the following section). Hence, the probable mechanism should be electron transfer. It can therefore be concluded that the uorescence quenching shown in Figs. 2 and 4 is purely caused by electron transfer. Scheme 2 represents a general idea showing the many stages involved in electron transfer from excited MgPc to quinone in solution.

[Q] x 10-3 M
Fig. 5. Comparison of SternVolmer plot for the time-resolved uorescence quenching of MgPc (1 10 5 M) by quinones in various concentrations (05 103 M) in acetonitrile. (For interpretation of the references to colour in this gure, the reader is referred to the web version of this article.)

3.5. Calculation of free energy changes (Get) for the electron transfer reactions The thermodynamics driving force ( G et ) of electron transfer reactions can also be veried according to the well-known Rehm Weller expression (Eq. (4)) [29]. The energy balance of a photoinduced electron transfer reaction is given by the RehmWeller equation, which combines the oxidation potential (Eox) of the electron donor, the reduction potential (Ered) of the electron acceptor, an electrostatic correction term C and the excited state energy of the sensitizer. Therefore, Rehm Weller equation remains valid for measurements of uorescence quenching through electron transfer.
ox red

the dynamic nature of quenching occurred. The quenching rate constants (kq) were calculated from the initial slopes of SternVolmer plots, and the values are complied in Table 2. Larger value of kq (1010 M 1 s 1, diffusion controlled limit) indicates efcient quenching of MgPc by quinones and the observed quenching is due to a diffusive process. The quenching rate constant follows the same order as shown below in both steady-state and time-resolved measurements: Naphthaquinone N benzoquinone N duroquinone Usually, quinones are good electron acceptors, but due to the presence of four methyl groups in its structure, duroquinone shows lesser quenching rate constant among the three. Benzoquinone shows the next higher quenching rate constant because it does not contain any substituent groups for decreasing the electron accepting nature like duroquinone. Comparing the three quinones, naphthaquinone shows the higher rate constant due to it having phenyl group with resonance (electron delocalization). Moreover, the effect of solvent on the quenching rate constant has also been studied. Time-resolved measurements show the most accurate results for the solvent effect. The decreasing order of quenching rate constant for the solvent effect is shown as follows: DMSO N CH3 CN N CH3 OH

Get E

E s C

is the oxidation potential of the donor, E(red) is the reduction where E(ox) potential of the acceptor (Table 3), Es is the excited state energy of the MgPc (1.82 eV) and C is the coulombic term. Since one of the species is neutral and the solvent used is polar in nature, the coulombic term in the above expression is neglected [30]. The Get values thus calculated for the ET processes in the systems studied in acetonitrile are all negative (Table 3). Hence, the ET process studied is thermodynamically favorable [31]. Thus, it is suggested that the observed quenching reaction involves an oxidative mechanism (i.e., electron transfer from excited MgPc to quinones).

350 1.0 300 0.8 250 200 150 0.4 100 0.2 50 0 350 420 490 560 630 700 770

From the above trend, we observed that while the solvent polarity decreases, quenching rate constant also decreases. 3.4. Analysis of quenching The uorescence quenching of MgPc by quinones may occur along four pathways: (i) the formation of (excited) charge transfer complex, (ii) energy transfer, (iii) proton transfer or (iv) electron transfer. To

Absorbance

0.6

DQ absorption MgPc emission

Table 2 Bimolecular quenching rate constant (kq) for MgPc in various from lifetime measurements. S. No Quinones kq / (1010 M1 s1) DMSO 1 2 3 Naphthaquinone Benzoquinone Duroquinone 4.97 4.51 3.78 CH3CN 2.25 2.22 1.91 CH3OH 1.41 1.24 1.08

0.0 280

Wavelength (nm)
Fig. 6. Emission spectra of MgPc (1 10 5 M) and absorption spectrum of duroquinone (5 103 M) in acetonitrile. (For interpretation of the references to colour in this gure, the reader is referred to the web version of this article.)

Intensity

192

M. Asha Jhonsi, A. Kathiravan / Journal of Molecular Liquids 194 (2014) 188192

D* + A

kd k
-d

(D*.....A)

k et k
-et

(D -.....A + )

k esc

D- + A+

h
D+A

kb
D.....A D = MgPc; A = Quinone

kR
Products

Scheme 2. A general scheme for electron transfer reactions of donor to acceptor, where kd and kd are the rate constants of diffusion and dissociation of the encounter complex, respectively. ket and ket is the activation controlled rate constants of electron transfer, and kesc is rate constant for the separation of radicals. kb is rate constant for the recombination of radical pair. kR is the rate constant for the decay of D radical.

Table 3 Electrochemical data and driving forces for electron transfer processes. S. No. 1 2 3
a b

Quinones Naphthaquinone Benzoquinone Duroquinone

E1/2 (V)a 0.82 0.48 0.84

G (eV)b 0.30 0.64 0.28

[2] [3] [4] [5] [6] [7] [8] [9] [10]

Reduction potential of quinones [32]. G is determined from RehmWeller equation. Oxidation potential of Mgphthalocyanine is +0.70 V vs SCE [33].

[11]

4. Conclusion The interaction between MgPc and quinone derivatives has been studied by UV-visible, steady-state and time-resolved uorescence spectroscopy. The results presented clearly indicated that, quinone quenches the uorescence of MgPc through dynamic process, since no ground-state complex is formed between MgPc and quinones. The quenching rate constants were calculated according to the relevant uorescence quenching data. The obtained quenching rate constants were in the order of 1010 M 1 s 1, which is in diffusion controlled limit indicates that occurrence of quenching process is efcient. Moreover, by decreasing solvent polarity quenching rate constant have also been decreases. The quenching mechanism was analyzed on the basis of exciplex formation, proton transfer, energy transfer and electron transfer. The data suggest that the quenching mechanism has been attributed to electron transfer from the excited state MgPc to the ground state quinones. Moreover, the negative Get value indicates the electron transfer processes studied are thermodynamically favorable. This fundamental work may be giving some hint in various emerging elds. Acknowledgments A.K. thanks the Department of Science and Technology, India, for DST-INSPIRE Faculty Award [IFA12-CH-78], Dt.: 01.02.2013. References
[1] B. Wardle, Principles and Applications of Photochemistry, John Wiley & Sons, Ltd, U. K., 2009

[12] [13] [14] [15] [16] [17] [18] [19] [20] [21] [22] [23] [24] [25] [26] [27] [28] [29] [30] [31] [32] [33]

C.D. Clark, M.Z. Hoffmann, Coord. Chem. Rev. 159 (1997) 359373. A.A. Alkaitis, G. Beck, M. Gratzel, J. Am. Chem. Soc. 97 (1975) 57235729. J. Gong, J. Liang, K. Sumathy, Renew. Sust. Energ. Rev. 16 (2012) 58485860. A. Mishra, M.K.R. Fischer, P. Buerle, Angew. Chem. Int. Ed. 48 (2009) 24742499 (48). S. Ardo, G.J. Meyer, Chem. Soc. Rev. 38 (2009) 115164. A. Hagfeldt, G. Boschloo, L. Sun, L. Kloo, H. Pettersson, Chem. Rev. 110 (2010) 65956663. M. Grtzel, Acc. Chem. Res. 42 (2009) 17881798. F. Gao, Y. Wang, D. Shi, J. Zhang, M. Wang, X. Jing, R. Humphry-Baker, P. Wang, S.M. Zakeeruddin, M. Grtzel, J. Am. Chem. Soc. 130 (2008) 1072010728. C.Y. Chen, M. Wang, J.Y. Li, N. Pootrakulchote, L. Alibabaei, C. Ngoc-le, J.D. Decoppet, J.H. Tsai, C. Grtzel, C.G. Wu, S.M. Zakeeruddin, M. Grtzel, ACS Nano 3 (2009) 31033109. L. Han, A. Islam, H. Chen, C. Malapaka, B. Chiranjeevi, S. Zhang, X. Yang, M. Yanagida, Energy Environ. Sci. 5 (2012) 60576060. A. Yella, H.-W. Lee, H.N. Tsao, C. Yi, A.K. Chandiran, M.K. Nazeeruddin, E.W.-G. Diau, C.-Y. Yeh, S.M. Zakeeruddin, M. Grtzel, Science 334 (2011) 629634. W. Zeng, Y. Cao, Y. Bai, Y. Wang, Y. Shi, M. Zhang, F. Wang, C. Pan, P. Wang, Chem. Mater. 22 (2010) 19151925. G. de La Torre, C.G. Claessens, T. Torres, Chem. Commun. (2007) 20002015. J. Mack, N. Kobayashi, Chem. Rev. 111 (2011) 281321. M.G. Walter, A.B. Rudine, C.C. Wamser, J. Porphyrins Phthalocyanines 14 (2010) 759792. M.K. Nazeeruddin, E. Hummphry-Baker, M. Grtzel, D. Whrle, G. Schnurpfeil, G. Schneider, A. Hirth, N. Trombach, J. Porphyrins Phthalocyanines 3 (1999) 230237. S. Eu, T. Kato, T. Ueyama, Y. Matano, H. Imahori, Dalton Trans. (2008) 54765483. S. Mori, M. Nagata, Y. Nakahata, K. Yasuta, R. Goto, M. Kimura, M. Taya, J. Am. Chem. Soc. 132 (2010) 40544055. M. Kimura, H. Nomoto, N. Masaki, S. Mori, Angew. Chem. Int. Ed. 51 (2012) 43714374. D. Sharma, G. Steen, J.P. Korterik, M. Garca-Iglesias, P. Vzquez, T. Torres, J.L. Herek, A. Huijser, J. Phys. Chem. C 117 (2013) 2539725404. H.Y. Yenilmez, A.M. Sevim, Z.A. Bayr, Synth. Met. 176 (2013) 1117. M. Gksel, M. Durmus, D. Atilla, J. Photochem. Photobiol. A Chem. 266 (2013) 3746. G. Gmrk, G.K. Karaolan, A. Erdomus, A. Gl, U. Avcata, Dyes Pigments 95 (2012) 280289. D. Dolphin (Ed.), The Porphyrins, Academic Press, New York, 1978. M.R. Gunner, P.L. Dutton, J. Am. Chem. Soc. 111 (1989) 34003412. J.R. Lakowicz, Principles of Fluorescence Spectroscopy, 3rd ed. Springer Publications, NewYork, USA, 2006. 278. A. Erdomus, M. Durmus, A.L. Uur, O. Avciata, U. Avciata, T. Nyokong, Synth. Met. 160 (2010) 18681876. D. Rehm, A. Weller, Isr. J. Chem. 8 (1970) 259271. S. Parret, F.M. Savary, J.P. Fouassier, P. Ramamurthy, J. Photochem. Photobiol. A Chem. 83 (1994) 205209. S. Nath, H. Pal, D.K. Palit, A.V. Sapre, J.P. Mittal, J. Phys. Chem. A 102 (1998) 58225830. N. Barboy, J. Feitelson, J. Phys. Chem. 88 (1984) 10651068. E. Ough, Z. Gasyna, M.J. Stillman, Inorg. Chem. 30 (1991) 23012310