Infrared Detection with Temperature Sweep for Stability Determination

Department of Chemistry and the Center for Photochemical Sciences, Bowling Green State University, Bowling ... Publication Date (Web): January 4, 2019...
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Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX

Infrared Detection with Temperature Sweep for Stability Determination of Ru-ON Metastable States Vasily Vorobyev,*,†,‡,§ Nina I. Alferova,‡ and Vyacheslav A. Emelyanov†,‡ †

Department of Natural Sciences, Novosibirsk State University, Novosibirsk 630090, Russia Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Science, Novosibirsk630090, Russia § Department of Chemistry and the Center for Photochemical Sciences, Bowling Green State University, Bowling Green, Ohio 43402, United States ‡

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S Supporting Information *

For most complexes, the O-coordinated nitrosyl has a lifetime of milliseconds before it converts back to the GS. Once photogenerated, MS1 can be stored for hours at temperatures below 150 K. The conventional definition of the “decay” temperature (Td) is a temperature when the “decay” rate constant is equal to 10−3 s−1.4 At elevated temperatures, a metastable state turns into the N-nitrosyl with a release of stored energy as heat. Precise measurements of the released heat give information about kinetics of MS-to-GS transformation (differential scanning calorimetry, DSC). The unimolecular nature of this transformation was proven for various complexes.7,8 However, the DSC measurements have limitations. If a temperature scan is too rapid, the exothermic reaction can promote itself. At low scan rates, the sensitivity may not be enough to detect the heat flow from MS decay. The unique feature of the coordinated nitrosyl is the valence vibration at 1700−2000 cm−1 along the N−O bond. The actual position of the GS absorption is dependent on the complex composition. The lower limit is 1840 cm−1. The frequency of the MS1 absorption is also dependent on the chemical nature of the complex and is related to the position of GS absorption band. Based on the list of complexes (Table S1 in the Supporting Information), the shift is 126 ± 15 cm−1 (Figure 2). The MS1 thermal stability can be derived from the

ABSTRACT: A novel method is proposed for studying the thermal decay of the oxygen-coordinated nitrosyl metastable states. Having examined 18 different ruthenium nitrosyl complexes, we observed that, upon photoinduced rotation from Ru-NO to Ru-ON coordination, the frequency of the nitrosyl valence bands shifts, on average, by 126 ± 15 cm−1. The thermal stability of the product Ru-ON state is qualitatively characterized (decay temperature, Arrhenius activation energy, and preexponential factor) using infrared absorption of the NO group, in comparison with the reference complex(es), which are all heated in the same KBr disk during temperature sweep.

S

everal ways are possible for a nitric oxide (NO) to bind to a metal center (Figure 1). In common cases, the nitrosyl

Figure 1. Potential energy surface of ruthenium nitrosyl complex, with respect to the formation of ground and metastable states at different Ru−N−O angles.

coordinates through the nitrogen atom. The oxygen-coordinated (MS1) and side-coordinated (MS2) states are metastable. These minor changes in NO bonding result in a drastic change in the visible and infrared absorption. For example, the yellow−orange crystal containing the stable ground-state species (GS) can be turned into the green crystal (MS1) by blue-light irradiation. Further near-infrared irradiation converts MS1 to MS2 with the crystal becoming black.1 Because of the highest thermal stability of MS among other metals, the ruthenium nitrosyl complexes are promising building blocks for the photochromic2 and photomagnetic materials.3 Further improvements are desirable because a few MS1 examples survive long enough at room temperature.4−6 © XXXX American Chemical Society

Figure 2. Correlation of the nitrosyl valence vibrations in the O- and N-coordinated states of complexes from Table S1 in the Supporting Information. Received: November 1, 2018

A

DOI: 10.1021/acs.inorgchem.8b03067 Inorg. Chem. XXXX, XXX, XXX−XXX

Communication

Inorganic Chemistry Arrhenius plot of the decay rates constants of MS1 absorption observed at various temperatures. The low reaction rates at low temperatures require hours of measurements; furthermore, the MS1 may fade away during the establishment of high temperature points. Thus, the isothermal IR measurement is limited to the ∼25 K temperature range. The dynamic nature of DSC provides valuable data in the 40 K window.9 Combining sensitivity of IR spectroscopy with the temperature sweep that covers a wider T range, compared with the one in DSC, is the goal of this study. This new method, applied to metastable states of the nitrosyl complexes, is presented below. The tested compounds are tabulated in Table 1 and Table S1. The MS1 stability in the complex 10 was derived from Table 1. Studied Complexes with MS1 Stability Ordered According to MS1 Nitrosyl Vibrational Frequency N

complex

synthetic reference

Tda (K) 258f 206, 188b 240c 182c 225c 197c 203c 214, 214b 233c 192d 181c 237c 254c 245g 220c 223c 239c 199c

1 2

trans-[RuNO(NH3)4OH]Cl2 trans-[RuNO(NH3)2(NO2)2OH]

10 11

3 4 5 6 7 8

cis-[{RuNO(NH3)2Cl2}2(H3O2)]Cl cis-Cs[RuNO(NH3)Cl4]·H2O mer-[RuNO(NH3)3Cl2]Cl·H2O mer(trans)-[RuNO(NH3)2Cl3] fac-[RuNO(NH3)2Cl3] cis-[RuNO(NH3)2(NO2)2OH]

12 d 13 14 15 16

tr-[RuNO(NH3)2Cl2(H2O)]Cl·2H2O fac-K2[RuNO(NO2)2Cl3] mer(cis)-[RuNO(NH3)2Cl3] mer-[RuNO(NH3)3Cl(H2O)]Cl2 tr-[RuNO(NH3)2(NO3)2(H2O)]NO3·H2O [RuNO(NH3)5]Cl3·H2O mer-[RuNO(NH3)3(NO2)(H2O)](NO3)2 fac-[RuNO(NH3)2(NO3)3] fac-[RuNO(NH3)3(NO2)2]NO3 fac-[RuNO(NH3)3(NO3)2]NO3·H2O

14 17 d 18 11 19 20 21 22 d

9 10 11 12 13 14 15 16 17 18

Figure 3. Evolution of the MS1 normalized absorption in the disk containing three complexes. The complexes 1, 3, and 14 (panel (A)) or 2, 8, and 18 (panel (B)) were mixed in the disk. The found temperature of the disk is displayed as a black line; the colored dots are experimental absorption data, and the colored lines are fits based on the discussed model.

(Figure 3A). The tetraammine complex 1 lasts the longest. The O-coordinated nitrosyl of diammine 3 and that of pentaammine 14 have similar stabilities. Qualitative thermal stability parameters of complexes can be obtained upon heating of the KBr disk, which, in addition to these complexes, contains a reference complex with known MS1 thermal stability (Ea and k0). As the heat propagates from the disk holder to the colder disk, the time dependence of the temperature rises from Tstart = 78 K to Tend = 293 K within the IR irradiation spot can be described by the following equation:

a

Td values found in this work. bIsothermal IR. cIR detection with temperature swipe. dSynthesis procedure is described in the Supporting Information. eDSC. fRef 5. gRef 23.

T (t ) = Tend + (T start − Tend) × e−kt

DSC of the irradiated samples; hereafter, 443 nm light was used. The isothermal infrared (IR) experiments were performed to determine the Arrhenius activation energy and the pre-exponential factor (Ea and k0) for metastable states of 2 and 8. Parameters of MS1 stability for 1 and 14 were taken from Woike and colleagues.5,23 Compounds 4, 11, and 18 are studied here for the first time. Detailed structures will be published later. The Ea and k0 values of MS1 in 3−7, 9, 11−13, and 15−18 are estimated by means of the new technique. The purified KBr (120 mg) was pressed into a disk with 2−3 complexes (1 mg each). Placed in the liquid nitrogen bath, the disk was irradiated for 5 min to generate MS1. Absorbance in 1700−2000 cm−1 range was monitored for detection of ν(NO) in Ru-ON when the cold disk was placed in the roomtemperature (rt) sample holder. Inspection of Figure 3 provides a qualitative conclusion regarding the relative stability of MS1 in different complexes embedded in the same KBr disk. The irradiated mixture of 1, 3, and 14 contains the MS1 bands at 1716, 1740, and 1799 cm1. Upon heating of the disk, the MS1 absorption bands decay according to the thermal stability of the individual MS1

where k is the heat rate constant and t is the time. The heat transfer from the disk holder to the disk is the solution of the differential equation that describes heating of an infinite cylinder (approximating the disk) from its side kept at fixed T. Since a powdered mixture of nitrosyl complexes and KBr is pressed together into the disk, the uncharacterized and reference complexes have the same temperature, because they share the same KBr surroundings. In such experimental settings, the reference compound acts as an internal temperature probe. The adsorbed water (up to 0.033%)24 gives IR baseline drift. A characteristic vertical shift of the baseline is observed at the ice-melting temperature (258.1 K), which is reproducible within 1.5 K and gives an additional T(t) point. A difference of 2.5 K from the minimum point on the KBr−water phase diagram (−12.6 °C)25 can be attributed to the local defects. Addition of nitrosyl complexes with the known MS decay to the same disk provides extra T(t) points; the entire T(t) curve becomes well-defined. The first-order kinetic model requires two fit variables, Ea and k0, to define a chosen MS1-to-GS B

DOI: 10.1021/acs.inorgchem.8b03067 Inorg. Chem. XXXX, XXX, XXX−XXX

Communication

Inorganic Chemistry

correlation coefficient is 0.54 and 0.52MS1−0.57GS). The ruthenium atomic charges by Hirshfeld31 in gas-phase GS or MS1 correlate better with Td to the level of 0.72−0.75. Moreover, the formal complex’s charge derived from rudimentary chemical structure correlates similarly (0.72) with Td. To study factors influencing the MS1 stability, studies should be focused on the isocharge series of ruthenium nitrosyl complexes. In summary, the presented results indicate that the proposed method is applicable for MS stability evaluations. The nitrosyl valence band shifts by 126 ± 15 cm−1 upon photoinduced NO rotation from N-to-O coordination in the studied ruthenium nitrosyl complexes. We developed a novel method to obtain quantitative results from the fitting of the IR bands fading away upon a heating sweep. The qualitative characterization of RuON thermal stability is possible by comparison with internal standards. For the studied 16 complexes (2−13, 15−18), the activation energy and pre-exponential frequency factor were obtained. The “decay” temperature (Td) that corresponds to an MS1-to-GS transformation rate of 10−3 s−1 and characterizes the stability of the O-coordinated isomers is estimated within 3 K accuracy and is found to be uncorrelated with the spectroscopic features of the studied complexes. The most pronounced correlation is that of Td with the DFT atomic charge on a ruthenium atom and is similar to the correlation of Td with the formal complex charge. Thus, to design ruthenium nitrosyl complexes with highly stable Ru-ON states, one should aim for the cationic compounds. The proposed IR detection method with temperature sweep is valuable for the design of photochromic or photomagnetic materials with enhanced MS1 thermal stability. It is also important for medical applications since the formation of the NO metastable states may be involved in the NO release.32

transformation when the temperature rises, according to the T(t) function. The MS1 bands can be separated into independent absorption datasets if the bands are at least 15−20 cm−1 apart from each other. Once separated, the MS1 absorption data in 1, 3, and 14 (Figure 3A) are fitted when using the described model. Since the Ea and k0 values are known for 1 and 14, the Ea and log(k0) for MS1 of 3 can be obtained and are equal to 69.0 kJ mol−1 and 12.0, respectively. The Td value, which is equal to 240 K, was calculated using the expression4 Td =

Ea R ln(k 0/0.001)

Next, we demonstrate that the spectral overlap of MS1 bands for the reference compounds is not a problem. The isomeric complexes 2 and 8 have two nonequivalent units in the solid phase with a 20−25 cm−1 difference in ν(NO). Each nonequivalent unit can be turned into MS1 and the 22 cm−1 gap remains. Both isomers have the overlapping MS1 band at 1758 cm−1. Conversely, we were able to fit the 1758 cm−1 band to obtain T(t) for the Ea and k0 determination of 18 based on 1818 cm−1 absorption (Figure 3B). Fitting the other two bands (1736 and 1780 cm−1) yielded the similar result. In the DSC measurements, accurate separation of the overlapping MS1 heat flows is not possible. A practitioner commonly uses DSC if the thermal stability must be known. The Ea and k0 values are derived from the modeling of released heat for the reaction under study. The irradiated samples of 5 and 18, chosen for the representative comparison between the DSC and proposed methods, were studied. The photogenerated Ru-ON states undergo exothermic conversion to the ground state at 250 or 238 K (Figure 4).

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.8b03067. Table S1 summarizing studied compounds; DSC studies of 10; isothermal IR studies of 2 and 8; KBr disk heating and data processing details; synthesis of 4, 11, and 18; plots of normalized MS1 absorption of the studied mixtures; schematic drawing of 1−18 (PDF)

Figure 4. Dots are DSC data for the complexes 5 and 18; the line fits are derived from the IR detection with temperature sweep.

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The heat flow for 5 and 18, calculated on the basis of the Ea and k0 parameters (found by the proposed method), is shown as lines. Visible resuts, the DSC results, and the modeled heat flow data are in perfect agreement. The change in the refractive index that accompanies the NO rotation finds application in the design of high-capacity memory devices.26 The question is whether high Td linkage isomers can be designed. For the series of pyridine complexes, the frequency of GS ν(NO) correlates with Td of MS1.27 Researchers witnessed the increase in the π-donating ability of the trans-to-NO-coordinated ligand that destabilizes the RuON state.28 In the computational study of trans-[RuNO(NH3)4L]2+, the first electronic transition calculated the MS1to-GS activation energy.29 Our data reveal that the MS1 and GS ν(NO) do not correlate with the decay temperature; the donating properties of trans-ligands correlates with Td similarly to the correlation of the HOMO−LUMO gap30 (Pearson’s

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Vasily Vorobyev: 0000-0002-7884-3724 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS Russian Foundation for Basic Research supported this study (Project No. 18-33-01223). The authors gratefully thank Dr. Alexander N. Tarnovsky and Ms. Laura M. Obloy, for help with the manuscript; Mr. Artem A. Mikhailov, for measuring isothermal IR kinetics; Dr. Gennadiy A. Kostin, for connecting the ice-melting point to the KBr-H2O diagram. C

DOI: 10.1021/acs.inorgchem.8b03067 Inorg. Chem. XXXX, XXX, XXX−XXX

Communication

Inorganic Chemistry

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(12) Vorobyev, V.; Emelyanov, V. A.; Valuev, I. A.; Baidina, I. A. Nitrosyl cis-dichlorodiammine ruthenium complex with bridging H3O2− ligand. Inorg. Chem. Commun. 2017, 76, 40. (13) Vorobyev, V.; Emelyanov, V. A.; Plusnina, O. A.; Makarov, E. M.; Baidina, I. A.; Smolentsev, A. I.; Tkachev, S. V.; Asanova, T. I. Triammine fac and mer Coordination for Ruthenium−Nitrosyl Complexes: Synthesis and Characterization of [RuNO(NH3)3Cl2]Cl. Eur. J. Inorg. Chem. 2017, 2017, 971. (14) Il’in, M. A.; Emel’yanov, V. A.; Baidina, I. A. Structure and synthesis of nitrosoruthenium trans-diammines [Ru(NO)(NH3)2Cl3] and [Ru(NO)(NH3)2(H2O)Cl2]Cl·H2O. J. Struct. Chem. 2008, 49 (6), 1090. (15) Sinitsyjn, N. M.; Svetlov, A. A.; Bryjkova, N. V. Synthesis and investigation into diammine complexes of nitrosylosmium and nitrosylruthenium. Koord. Khim. 1976, 2 (5), 662. (16) Vorobyev, V.; Kostin, G. A.; Kuratieva, N. V.; Emelyanov, V. A. Two Oxygen-Coordinated Metastable Ru−ON States for Ruthenium Mononitrosyl Complex. Inorg. Chem. 2016, 55 (18), 9158. (17) Emel’yanov, V. A.; Baidina, I. A.; Gromilov, S. A.; Virovets, A. V.; Belyaev, A. V. Synthesis, Formation Mechanism, and Crystal Structure of the Nitrosoruthenium(II) Nitrochloride Complex FacK2[RuNO(NO2)2Cl3]. J. Struct. Chem. 2002, 43 (2), 304. (18) Emel’yanov, V. A.; Baidina, I. A.; Gromilov, S. A.; Vasiliev, A. D.; Belyaev, A. V. Synthesis and Crystal Structure of Nitrosoruthenium Triammino Complex [RuNO(NH3)3Cl(H2O)]Cl2. J. Struct. Chem. 2000, 41 (6), 1030. (19) Il’in, M. A.; Emel’yanov, V. A.; Baidina, I. A.; Alferova, N. I.; Korol’kov, I. V. Study of nitrosation of hexaammineruthenium(II): Crystal structure of trans-[RuNO(NH3)4Cl]Cl2. Russ. J. Inorg. Chem. 2007, 52 (1), 62. (20) Vorobyev, V.; Kabin, E. V.; Emelyanov, V. A.; Baidina, I. A.; Korolkov, I. V. Synthesis and crystal structure of mernitroaquatriamminenitrosylruthenium(II) nitrate [RuNO(NH3)3(NO2)(H2O)](NO3)2. Inorg. Chem. Commun. 2016, 68, 1. (21) Kabin, E. V.; Emel’yanov, V. A.; Vorob’yev, V. A.; Alferova, N. I.; Tkachev, S. V.; Baidina, I. A. Reaction of trans-[RuNO(NH3)4(OH)]Cl2 with nitric acid and synthesis of ammine (nitrato)nitrosoruthenium complexes. Russ. J. Inorg. Chem. 2012, 57 (8), 1146. (22) Vorobyev, V.; Baidina, I. A.; Korolkov, I. V.; Emelyanov, V. A. Unpublished work. (23) Schaniel, D.; Woike, T.; Boskovic, C.; Güdel, H. U. Evidence for two light-induced metastable states in Cl3[Ru(NH3)5NO]H2O. Chem. Phys. Lett. 2004, 390 (4−6), 347. (24) Van der Maas, J. H.; Tolk, A. The influence of moisture on potassium bromide disks used in infrared spectrometry. Spectrochim. Acta 1962, 18 (2), 235. (25) Holmberg, K. E.; Heikkilä, J.; Beagley, B.; Aalto, T.; Werner, P.E.; Junggren, U.; Lamm, B.; Samuelsson, B. Phase Diagrams of Some Sodium and Potassium Salts in Light and Heavy Water. Acta Chem. Scand. 1969, 23 (2), 467. (26) (a) Woike, T.; Haussühl, S.; Sugg, B.; Rupp, R. A.; Beckers, J.; Imlau, M.; Schieder, R. Phase gratings in the visible and near-infrared spectral range realized by metastable electronic states in Na2[Fe(CN)5NO]·2H2O. Appl. Phys. B: Lasers Opt. 1996, 63 (3), 243. (b) Cormary, B.; Malfant, I. Compositions of photoswitchable materials. U.S. Patent No. 9,880,323, 2018. (27) Fomitchev, D. V.; Coppens, P. Light-induced metastable linkage isomers of transition metal nitrosyls. Comments Inorg. Chem. 1999, 21 (1−3), 131. (28) Coppens, P.; Novozhilova, I.; Kovalevsky, A. Photoinduced linkage isomers of transition-metal nitrosyl compounds and related complexes. Chem. Rev. 2002, 102 (4), 861. (29) Yamaletdinov, R. D.; Zilberberg, I. L. The Effect of trans Ligands in the NO-Linkage Reverse Isomerization for Ruthenium− Nitrosyl−Tetraammine Complexes: A DFT Study. Eur. J. Inorg. Chem. 2017, 2017 (23), 2951. (30) For VWM functional with TZP basis set, and gas-phase calculations, see: (a) Vosko, S. H.; Wilk, L.; Nusair, M. Accurate spindependent electron liquid correlation energies for local spin density

REFERENCES

(1) Cormary, B.; Ladeira, S.; Jacob, K.; Lacroix, P. G.; Woike, T.; Schaniel, D.; Malfant, I. Structural Influence on the Photochromic Response of a Series of Ruthenium Mononitrosyl Complexes. Inorg. Chem. 2012, 51 (14), 7492. (2) (a) Cormary, B.; Malfant, I.; Valade, L. New photochromic xerogels composites based on nitrosyl complexes. J. Sol-Gel Sci. Technol. 2009, 52, 19−23. (b) Kushch, L. A.; Yagubskii, E. B.; Dmitriev, A. I.; Morgunov, R. B.; Emel’yanov, V. A.; Mustafina, A. R.; Gubaidullin, A. T.; Burilov, V. A.; Solovieva, S. E.; Schaniel, D.; Woike, T. Bifunctional supramolecular systems on the platform of psulfonatothiacalix[4]arene containing photochromic mononitrosyl Ru (II) and paramagnetic aqua Gd or Dy complexes. Phys. B 2010, 405 (11), S30. (c) Imlau, M.; Haussühl, S.; Woike, T.; Schieder, R.; Angelov, V.; Rupp, R. A.; Schwarz, K. Holographic recording by excitation of metastable electronic states in Na2[Fe(CN)5NO]·2H2O: a new photorefractive effect. Appl. Phys. B: Lasers Opt. 1999, 68 (5), 877. (3) (a) Kushch, L. A.; Sasnovskaya, V. D.; Yagubskii, E. B.; Dmitriev, A. I.; Morgunov, R. B.; Emel’yanov, V. A.; Woike, T. Photochromic single-molecule magnets based on oxocarboxylate Mn 12 clusters and mononitrosyl Ru complexes. Russ. Chem. Bull. 2011, 60 (6), 1078. (b) Kushch, L. A.; Emel’yanov, V. A.; Golhen, S.; Cador, O.; Schaniel, D.; Woike, T.; Ouahab, L.; Yagubskii, E. B. The photochromic paramagnet derived from polyoxometalate [Cr(OH)6Mo6O18]3− and ruthenium mononitrosyl complex [RuNO(en)2Cl]2+. Inorg. Chim. Acta 2009, 362 (7), 2279. (c) Kushch, L. A.; Kurochkina, L. S.; Yagubskii, E. B.; Shilov, G. V.; Aldoshin, S. M.; Emel’yanov, V. A.; Shvachko, Y. N.; Mironov, V. S.; Schaniel, D.; Woike, T.; Carbonera, C.; Mathonière, C. Bifunctional materials based on the photochromic cation [RuNO(NH3)5]3+ with paramagnetic metal complex anions. Eur. J. Inorg. Chem. 2006, 2006, 4074. (4) Morioka, Y.; Ishikawa, A.; Tomizawa, H.; Miki, E. I. Lightinduced metastable states in nitrosyl−ruthenium complexes containing ethylenediamine and oxalate ion ligands. J. Chem. Soc., Dalton Trans. 2000, 5, 781. (5) Schaniel, D.; Woike, T.; Delley, B.; Boskovic, C.; Biner, D.; Krämer, K. W.; Güdel, H.-U. Long-lived light-induced metastable states in trans-[Ru(NH3)4(H2O)NO]Cl3·H2O and related compounds. Phys. Chem. Chem. Phys. 2005, 7 (6), 1164. (6) Kostin, G.; Mikhailov, A.; Kuratieva, N.; Pishchur, D. P.; Makhinya, A. High thermal stability of the Ru-ON (MS1) linkage isomer of ruthenium nitrosyl complex [RuNO(Py)4F](ClO4)2 with trans NO-Ru-F coordinate. New J. Chem. 2018, DOI: 10.1039/ C8NJ04620D. (7) (a) Woike, T.; Haussü hl, S. Infrared-spectroscopic and differential scanning calorimetric studies of the two light-induced metastable states in K2[Ru(NO2)4(OH)(NO)]. Solid State Commun. 1993, 86 (5), 333. (b) Ferlay, S.; Schmalle, H. W.; Francese, G.; Stoeckli-Evans, H.; Imlau, M.; Schaniel, D.; Woike, T. Light-induced metastable states in oxalatenitrosylruthenium(II) and terpyridinenitrosylruthenium(II) complexes. Inorg. Chem. 2004, 43 (11), 3500. (8) Vorobyev, V.; Kostin, G. A.; Kuratieva, N. V.; Emelyanov, V. A. Two Oxygen-Coordinated Metastable Ru−ON States for Ruthenium Mononitrosyl Complex. Inorg. Chem. 2016, 55 (18), 9158. (9) Kostin, G. A.; Borodin, A. O.; Mikhailov, A. A.; Kuratieva, N. V.; Kolesov, B. A.; Pishchur, D. P.; Woike, T.; Schaniel, D. Photocrystallographic, Spectroscopic, and Calorimetric Analysis of LightInduced Linkage NO Isomers in [RuNO(NO2)2(pyridine)2OH]. Eur. J. Inorg. Chem. 2015, 2015, 4905. (10) Il’yin, M. A.; Emel’anov, V. A.; Belyaev, A. V.; Makhinya, A. N.; Tkachev, S. V.; Alferova, N. I. New method for the synthesis of transhydroxotetraamminenitrosoruthenium(II) dichloride and its characterization. Russ. J. Inorg. Chem. 2008, 53 (7), 1070. (11) Il’in, M. A.; Kabin, E. V.; Emel’yanov, V. A.; Baidina, I. A.; Vorob’yov, V. A. trans-dinitro-and trans-dinitratoruthenium complexes [RuNO(NH3)2(NO2)2(OH)] and [RuNO(NH3)2(H2O)(NO3)2]NO3·H2O. J. Struct. Chem. 2009, 50 (2), 328. D

DOI: 10.1021/acs.inorgchem.8b03067 Inorg. Chem. XXXX, XXX, XXX−XXX

Communication

Inorganic Chemistry calculations: a critical analysis. Can. J. Phys. 1980, 58 (8), 1200. (b) Van Lenthe, E.; Baerends, E. J. Optimized Slater-type basis sets for the elements 1−118. J. Comput. Chem. 2003, 24, 1142. For the ADF program set, see: (c) Te Velde, G. T.; Bickelhaupt, F. M.; Baerends, E. J.; Fonseca Guerra, C.; van Gisbergen, S. J.; Snijders, J. G.; Ziegler, T. Chemistry with ADF. J. Comput. Chem. 2001, 22 (9), 931. (d) Fonseca Guerra, C.; Snijders, J. G.; Te Velde, G.; Baerends, E. J. Towards an order-N DFT method. Theor. Chem. Acc. 1998, 99 (6), 391. (e) ADF2013, SCM Theoretical Chemistry; Vrije Universiteit: Amsterdam, The Netherlands, http://www.scm.com, 2013. (31) (a) Hirshfeld, F. L. Bonded-atom fragments for describing molecular charge densities. Theor. Chim. Acta 1977, 44 (2), 129. (b) Wiberg, K. B.; Rablen, P. R. Comparison of atomic charges derived via different procedures. J. Comput. Chem. 1993, 14 (12), 1504. (32) (a) García, J. S.; Alary, F.; Boggio-Pasqua, M.; Dixon, I. M.; Heully, J. L. Is photoisomerization required for NO photorelease in ruthenium nitrosyl complexes? J. Mol. Model. 2016, 22 (11), 284. (b) Mir, J. M.; Jain, N.; Jaget, P. S.; Maurya, R. C. Density functionalized [RuII(NO)(Salen)(Cl)] complex: Computational photodynamics and in vitro anticancer facets. Photodiagn. Photodyn. Ther. 2017, 19, 363.

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DOI: 10.1021/acs.inorgchem.8b03067 Inorg. Chem. XXXX, XXX, XXX−XXX