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Nina P. Gritsan - One of the best experts on this subject based on the ideXlab platform.
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Photochemistry of Tetrasulfur Tetranitride: Laser Flash Photolysis and Quantum Chemical Study.
ChemInform, 2012Co-Authors: Elena A. Pritchina, Daria S Terpilovskaya, Yuri P Tsentalovich, Matthew S Platz, Nina P. GritsanAbstract:The photochemistry of S4N4 with a highly symmetric cage structure is studied by laser flash photolysis and B3LYP quantum chemical computations.
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Photochemistry of Tetrasulfur Tetranitride: Laser Flash Photolysis and Quantum Chemical Study
Inorganic chemistry, 2012Co-Authors: Elena A. Pritchina, Daria S Terpilovskaya, Yuri P Tsentalovich, Matthew S Platz, Nina P. GritsanAbstract:The photochemistry of Tetrasulfur tetranitride (1) was studied in hexane solution by the laser flash photolysis technique (LFP). The experimental findings were interpreted using the results of previous matrix isolation studies (Pritchina, E.A.; Gritsan, N.P.; Bally, T.; Zibarev, A.V. Inorg. Chem. 2009, 48, 4075) and high-level quantum chemical calculations. LFP produces two primary intermediates, one of which is the boat-shaped 8-membered cyclic compound (2) and the other is the 6-membered S(3)N(3) cyclic compound carrying an exocyclic (S)-N═S group (3). The primary products 2 and 3 absorb a second photon and undergo transformation to the 6-membered S(3)N(3) cycle carrying an exocyclic (N)-S≡N group (4), which is very unstable and converts back to intermediate 3. The quantum yield of the primary product formation is close to unity even though the quantum yield of photodegradation of 1 is low (~0.01). Thus, 1 is a photochromic compound undergoing in solution the thermally reversible photochemical isomerization. The mechanism of the photochromic process was established, and the rate constants of the elementary reactions were measured.
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photochemistry of Tetrasulfur tetranitride laser flash photolysis and quantum chemical study
Inorganic Chemistry, 2012Co-Authors: Elena A. Pritchina, Daria S Terpilovskaya, Yuri P Tsentalovich, Matthew S Platz, Nina P. GritsanAbstract:The photochemistry of Tetrasulfur tetranitride (1) was studied in hexane solution by the laser flash photolysis technique (LFP). The experimental findings were interpreted using the results of previous matrix isolation studies (Pritchina, E.A.; Gritsan, N.P.; Bally, T.; Zibarev, A.V. Inorg. Chem.2009, 48, 4075) and high-level quantum chemical calculations. LFP produces two primary intermediates, one of which is the boat-shaped 8-membered cyclic compound (2) and the other is the 6-membered S3N3 cyclic compound carrying an exocyclic (S)–N═S group (3). The primary products 2 and 3 absorb a second photon and undergo transformation to the 6-membered S3N3 cycle carrying an exocyclic (N)–S≡N group (4), which is very unstable and converts back to intermediate 3. The quantum yield of the primary product formation is close to unity even though the quantum yield of photodegradation of 1 is low (∼0.01). Thus, 1 is a photochromic compound undergoing in solution the thermally reversible photochemical isomerization. The...
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Photochemistry of Tetrasulfur Tetranitride: Laser Flash Photolysis and Quantum Chemical Study
2012Co-Authors: Elena A. Pritchina, Daria S Terpilovskaya, Yuri P Tsentalovich, Matthew S Platz, Nina P. GritsanAbstract:The photochemistry of Tetrasulfur tetranitride (1) was studied in hexane solution by the laser flash photolysis technique (LFP). The experimental findings were interpreted using the results of previous matrix isolation studies (Pritchina, E.A.; Gritsan, N.P.; Bally, T.; Zibarev, A.V. Inorg. Chem. 2009, 48, 4075) and high-level quantum chemical calculations. LFP produces two primary intermediates, one of which is the boat-shaped 8-membered cyclic compound (2) and the other is the 6-membered S3N3 cyclic compound carrying an exocyclic (S)–NS group (3). The primary products 2 and 3 absorb a second photon and undergo transformation to the 6-membered S3N3 cycle carrying an exocyclic (N)–SN group (4), which is very unstable and converts back to intermediate 3. The quantum yield of the primary product formation is close to unity even though the quantum yield of photodegradation of 1 is low (∼0.01). Thus, 1 is a photochromic compound undergoing in solution the thermally reversible photochemical isomerization. The mechanism of the photochromic process was established, and the rate constants of the elementary reactions were measured
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Photochemical Study on the Reactivity of Tetrasulfur Tetranitride, S4N4
Inorganic Chemistry, 2009Co-Authors: Elena A. Pritchina, Andrey V. Zibarev, Nina P. Gritsan, Thomas BallyAbstract:To elucidate the multifaceted but poorly understood chemistry of the pivotal polysulfur−nitrogen heterocycle, Tetrasulfur tetranitride (S4N4, 1), its photochemistry was studied in Ar matrices. Thereby two primary intermediates and a secondary one (2−4) were detected, and their UV−vis and IR spectra were identified through specific interconversions of 1−4 that can be induced by selective irradiations. The structures associated with these spectra were assigned with the help of DFT calculations. From these assignments it follows that, under the conditions of the present experiments, the cage structure of 1 transforms into isomeric structures 2−4, one of which is a boat-shaped 8-membered cycle (2), and the two other are novel 6-membered S3N3 cycles carrying exocyclic (N)—S≡N (3) or (S)—N═S (4) groups, respectively, which have not been previously described. These three intermediates probably play a pivotal role in the formation of the diverse products that are observed in the reactions of S4N4 even under mild ...
Elena A. Pritchina - One of the best experts on this subject based on the ideXlab platform.
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Photochemistry of Tetrasulfur Tetranitride: Laser Flash Photolysis and Quantum Chemical Study.
ChemInform, 2012Co-Authors: Elena A. Pritchina, Daria S Terpilovskaya, Yuri P Tsentalovich, Matthew S Platz, Nina P. GritsanAbstract:The photochemistry of S4N4 with a highly symmetric cage structure is studied by laser flash photolysis and B3LYP quantum chemical computations.
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Photochemistry of Tetrasulfur Tetranitride: Laser Flash Photolysis and Quantum Chemical Study
Inorganic chemistry, 2012Co-Authors: Elena A. Pritchina, Daria S Terpilovskaya, Yuri P Tsentalovich, Matthew S Platz, Nina P. GritsanAbstract:The photochemistry of Tetrasulfur tetranitride (1) was studied in hexane solution by the laser flash photolysis technique (LFP). The experimental findings were interpreted using the results of previous matrix isolation studies (Pritchina, E.A.; Gritsan, N.P.; Bally, T.; Zibarev, A.V. Inorg. Chem. 2009, 48, 4075) and high-level quantum chemical calculations. LFP produces two primary intermediates, one of which is the boat-shaped 8-membered cyclic compound (2) and the other is the 6-membered S(3)N(3) cyclic compound carrying an exocyclic (S)-N═S group (3). The primary products 2 and 3 absorb a second photon and undergo transformation to the 6-membered S(3)N(3) cycle carrying an exocyclic (N)-S≡N group (4), which is very unstable and converts back to intermediate 3. The quantum yield of the primary product formation is close to unity even though the quantum yield of photodegradation of 1 is low (~0.01). Thus, 1 is a photochromic compound undergoing in solution the thermally reversible photochemical isomerization. The mechanism of the photochromic process was established, and the rate constants of the elementary reactions were measured.
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photochemistry of Tetrasulfur tetranitride laser flash photolysis and quantum chemical study
Inorganic Chemistry, 2012Co-Authors: Elena A. Pritchina, Daria S Terpilovskaya, Yuri P Tsentalovich, Matthew S Platz, Nina P. GritsanAbstract:The photochemistry of Tetrasulfur tetranitride (1) was studied in hexane solution by the laser flash photolysis technique (LFP). The experimental findings were interpreted using the results of previous matrix isolation studies (Pritchina, E.A.; Gritsan, N.P.; Bally, T.; Zibarev, A.V. Inorg. Chem.2009, 48, 4075) and high-level quantum chemical calculations. LFP produces two primary intermediates, one of which is the boat-shaped 8-membered cyclic compound (2) and the other is the 6-membered S3N3 cyclic compound carrying an exocyclic (S)–N═S group (3). The primary products 2 and 3 absorb a second photon and undergo transformation to the 6-membered S3N3 cycle carrying an exocyclic (N)–S≡N group (4), which is very unstable and converts back to intermediate 3. The quantum yield of the primary product formation is close to unity even though the quantum yield of photodegradation of 1 is low (∼0.01). Thus, 1 is a photochromic compound undergoing in solution the thermally reversible photochemical isomerization. The...
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Photochemistry of Tetrasulfur Tetranitride: Laser Flash Photolysis and Quantum Chemical Study
2012Co-Authors: Elena A. Pritchina, Daria S Terpilovskaya, Yuri P Tsentalovich, Matthew S Platz, Nina P. GritsanAbstract:The photochemistry of Tetrasulfur tetranitride (1) was studied in hexane solution by the laser flash photolysis technique (LFP). The experimental findings were interpreted using the results of previous matrix isolation studies (Pritchina, E.A.; Gritsan, N.P.; Bally, T.; Zibarev, A.V. Inorg. Chem. 2009, 48, 4075) and high-level quantum chemical calculations. LFP produces two primary intermediates, one of which is the boat-shaped 8-membered cyclic compound (2) and the other is the 6-membered S3N3 cyclic compound carrying an exocyclic (S)–NS group (3). The primary products 2 and 3 absorb a second photon and undergo transformation to the 6-membered S3N3 cycle carrying an exocyclic (N)–SN group (4), which is very unstable and converts back to intermediate 3. The quantum yield of the primary product formation is close to unity even though the quantum yield of photodegradation of 1 is low (∼0.01). Thus, 1 is a photochromic compound undergoing in solution the thermally reversible photochemical isomerization. The mechanism of the photochromic process was established, and the rate constants of the elementary reactions were measured
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Photochemical Study on the Reactivity of Tetrasulfur Tetranitride, S4N4
Inorganic Chemistry, 2009Co-Authors: Elena A. Pritchina, Andrey V. Zibarev, Nina P. Gritsan, Thomas BallyAbstract:To elucidate the multifaceted but poorly understood chemistry of the pivotal polysulfur−nitrogen heterocycle, Tetrasulfur tetranitride (S4N4, 1), its photochemistry was studied in Ar matrices. Thereby two primary intermediates and a secondary one (2−4) were detected, and their UV−vis and IR spectra were identified through specific interconversions of 1−4 that can be induced by selective irradiations. The structures associated with these spectra were assigned with the help of DFT calculations. From these assignments it follows that, under the conditions of the present experiments, the cage structure of 1 transforms into isomeric structures 2−4, one of which is a boat-shaped 8-membered cycle (2), and the two other are novel 6-membered S3N3 cycles carrying exocyclic (N)—S≡N (3) or (S)—N═S (4) groups, respectively, which have not been previously described. These three intermediates probably play a pivotal role in the formation of the diverse products that are observed in the reactions of S4N4 even under mild ...
Kyongtae Kim - One of the best experts on this subject based on the ideXlab platform.
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Total synthesis of 3,3′:4′,3″-ter-1,2,5-thiadiazole using a synthetic utility of S4N4·SbCl5 complex
Tetrahedron, 2007Co-Authors: Kil-joong Kim, Kyongtae KimAbstract:Abstract 3,3′:4′,3″-Ter-1,2,5-thiadiazole, an useful oligoheterocyclic compound, has been accomplished in seven steps from 1-(5-methyl-3-isoxazolyl)ethanone or diethyl acetylenedicarboxylate using a synthetic utility of Tetrasulfur tetranitride antimony pentachloride (S4N4·SbCl5) complex to make a 1,2,5-thiadiazole ring.
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Reactions of (Aryl)(chloro)methyl p-Tolyl Sulfoxides with Tetrasulfur Tetranitride (S4N4): Formation and Characterization of 3,5-Diaryl-1,2,4,6-thiatriazine 1-Oxides
Tetrahedron, 2000Co-Authors: Yung Cheol Kong, Kyongtae Kim, Yung Ja ParkAbstract:Abstract The reactions of (aryl)(chloro)methyl p-tolyl sulfoxides 2 with Tetrasulfur tetranitride (S4N4) in p-dioxane at reflux gave 3,5-diaryl-1,2,4,6-thiatriazine 1-oxides, 3,5-diaryl-1,2,4-thiadiazoles, and 1-amino-3,5-diaryl-1,2,4,6-thiatriazine 1-oxides. For the first time, the structures of 3,5-diaryl-1,2,4,6-thiatriazine 1-oxides were unequivocally characterized based on X-ray crystallography of 3,5-di(3,4-dimethylphenyl)-1,2,4,6-thiatriazine 1-oxide. Treatment of the thiatriazine 1-oxides with m-CPBA gave 2,6-diaryl-4-(3-chlorophenyl)-1,3,5-triazines. Mechanisms are proposed for the formation of thiatriazine 1-oxides and 1,3,5-triazines.
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REACTIONS OF ARYLGLYOXALS WITH Tetrasulfur TETRANITRIDES (S4N4) : FORMATION OF 2-AROYL-5-ARYLIMIDAZOLES AND 2-AROYL-5-ARYLOXAZOLES
Journal of Heterocyclic Chemistry, 1999Co-Authors: Yung Cheol Kong, Kyongtae KimAbstract:Treatment of arylglyoxal monohydrates with Tetrasulfur tetranitride in p-dioxane at reflux afforded 2-aroyl-5-arylimidizoles and 2-aroyl-5-aryloxazoles in 10 to 31% and 17 to 32% yields, respectively. With non-hydrate of arylglyoxals, yields of the latter increase somewhat, whereas essentially no changes in yields of the former were observed. A mechanism is proposed for the formation of the products.
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Reactions of 5-substituted 3-alkyl- and 3-aryl-isoxazoles with Tetrasulfur tetranitride antimony pentachloride complex (S4N4·SbCl5): complete regioselective formation of 4-substituted 3-acyl- and 3-aroyl-1,2,5-thiadiazoles and their mechanism of form
Journal of the Chemical Society Perkin Transactions 1, 1998Co-Authors: Kil-joong Kim, Kyongtae KimAbstract:The reactions of 3-alkyl- 5a–f, 3-aryl- 5g–m, 3-acylamido- 5n,p, 3-benzamido- 5o and 3-arylamino- 5q -5-alkyl- and -5-aryl-isoxazoles with Tetrasulfur tetranitride antimony pentachloride complex (S4N4·SbCl5) in toluene at 90 °C to reflux temperature give 3-acyl- 6a–c, e, n–q and 3-aroyl-4-substituted-1,2,5-thiadiazoles 6d, f–m in 13 to 61% yields as single isomers. The same reactions of 3,4-dimethyl- 5s, 5v, 4-ethyl-3-methyl- 5t -5-alkyl- and/or 5-aryl-isoxazoles under the same conditions give 3-(1-acetyl-1-chloroethyl)- 8a, 3-(1-benzoyl-1-chloropropyl)- 8b, 3-(1-benzoyl-1-chloroethyl)- 8d, or 3-(1-benzoyl-1-chloroethyl)-4-methyl-1,2,5-thiadiazoles 8c, which are a new type of 1,2,5-thiadiazole derivatives. In addition the reactions with 5-aryl-4-bromoisoxazoles (5,w,y,z) having an electron-donating substituent such as methyl, 4-methylphenyl, and 4-methoxyphenyl groups at C3 under the same conditions afford 3-aroyl-4-substituted-1,2,5-thiadiazoles 6d, 6j and 6k, whereas the starting isoxazoles are recovered from the reactions with 5-aryl-4-bromoisoxazoles 5x,z′ having a phenyl or a 4-chlorophenyl group at C3. A plausible mechanism is proposed for the formation of the products.
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reactions of 5 substituted 3 alkyl and 3 aryl isoxazoles with Tetrasulfur tetranitride antimony pentachloride complex s4n4 sbcl5 complete regioselective formation of 4 substituted 3 acyl and 3 aroyl 1 2 5 thiadiazoles and their mechanism of formation
Journal of The Chemical Society-perkin Transactions 1, 1998Co-Authors: Kil-joong Kim, Kyongtae KimAbstract:The reactions of 3-alkyl- 5a–f, 3-aryl- 5g–m, 3-acylamido- 5n,p, 3-benzamido- 5o and 3-arylamino- 5q -5-alkyl- and -5-aryl-isoxazoles with Tetrasulfur tetranitride antimony pentachloride complex (S4N4·SbCl5) in toluene at 90 °C to reflux temperature give 3-acyl- 6a–c, e, n–q and 3-aroyl-4-substituted-1,2,5-thiadiazoles 6d, f–m in 13 to 61% yields as single isomers. The same reactions of 3,4-dimethyl- 5s, 5v, 4-ethyl-3-methyl- 5t -5-alkyl- and/or 5-aryl-isoxazoles under the same conditions give 3-(1-acetyl-1-chloroethyl)- 8a, 3-(1-benzoyl-1-chloropropyl)- 8b, 3-(1-benzoyl-1-chloroethyl)- 8d, or 3-(1-benzoyl-1-chloroethyl)-4-methyl-1,2,5-thiadiazoles 8c, which are a new type of 1,2,5-thiadiazole derivatives. In addition the reactions with 5-aryl-4-bromoisoxazoles (5,w,y,z) having an electron-donating substituent such as methyl, 4-methylphenyl, and 4-methoxyphenyl groups at C3 under the same conditions afford 3-aroyl-4-substituted-1,2,5-thiadiazoles 6d, 6j and 6k, whereas the starting isoxazoles are recovered from the reactions with 5-aryl-4-bromoisoxazoles 5x,z′ having a phenyl or a 4-chlorophenyl group at C3. A plausible mechanism is proposed for the formation of the products.
Daria S Terpilovskaya - One of the best experts on this subject based on the ideXlab platform.
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Photochemistry of Tetrasulfur Tetranitride: Laser Flash Photolysis and Quantum Chemical Study.
ChemInform, 2012Co-Authors: Elena A. Pritchina, Daria S Terpilovskaya, Yuri P Tsentalovich, Matthew S Platz, Nina P. GritsanAbstract:The photochemistry of S4N4 with a highly symmetric cage structure is studied by laser flash photolysis and B3LYP quantum chemical computations.
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photochemistry of Tetrasulfur tetranitride laser flash photolysis and quantum chemical study
Inorganic Chemistry, 2012Co-Authors: Elena A. Pritchina, Daria S Terpilovskaya, Yuri P Tsentalovich, Matthew S Platz, Nina P. GritsanAbstract:The photochemistry of Tetrasulfur tetranitride (1) was studied in hexane solution by the laser flash photolysis technique (LFP). The experimental findings were interpreted using the results of previous matrix isolation studies (Pritchina, E.A.; Gritsan, N.P.; Bally, T.; Zibarev, A.V. Inorg. Chem.2009, 48, 4075) and high-level quantum chemical calculations. LFP produces two primary intermediates, one of which is the boat-shaped 8-membered cyclic compound (2) and the other is the 6-membered S3N3 cyclic compound carrying an exocyclic (S)–N═S group (3). The primary products 2 and 3 absorb a second photon and undergo transformation to the 6-membered S3N3 cycle carrying an exocyclic (N)–S≡N group (4), which is very unstable and converts back to intermediate 3. The quantum yield of the primary product formation is close to unity even though the quantum yield of photodegradation of 1 is low (∼0.01). Thus, 1 is a photochromic compound undergoing in solution the thermally reversible photochemical isomerization. The...
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Photochemistry of Tetrasulfur Tetranitride: Laser Flash Photolysis and Quantum Chemical Study
Inorganic chemistry, 2012Co-Authors: Elena A. Pritchina, Daria S Terpilovskaya, Yuri P Tsentalovich, Matthew S Platz, Nina P. GritsanAbstract:The photochemistry of Tetrasulfur tetranitride (1) was studied in hexane solution by the laser flash photolysis technique (LFP). The experimental findings were interpreted using the results of previous matrix isolation studies (Pritchina, E.A.; Gritsan, N.P.; Bally, T.; Zibarev, A.V. Inorg. Chem. 2009, 48, 4075) and high-level quantum chemical calculations. LFP produces two primary intermediates, one of which is the boat-shaped 8-membered cyclic compound (2) and the other is the 6-membered S(3)N(3) cyclic compound carrying an exocyclic (S)-N═S group (3). The primary products 2 and 3 absorb a second photon and undergo transformation to the 6-membered S(3)N(3) cycle carrying an exocyclic (N)-S≡N group (4), which is very unstable and converts back to intermediate 3. The quantum yield of the primary product formation is close to unity even though the quantum yield of photodegradation of 1 is low (~0.01). Thus, 1 is a photochromic compound undergoing in solution the thermally reversible photochemical isomerization. The mechanism of the photochromic process was established, and the rate constants of the elementary reactions were measured.
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Photochemistry of Tetrasulfur Tetranitride: Laser Flash Photolysis and Quantum Chemical Study
2012Co-Authors: Elena A. Pritchina, Daria S Terpilovskaya, Yuri P Tsentalovich, Matthew S Platz, Nina P. GritsanAbstract:The photochemistry of Tetrasulfur tetranitride (1) was studied in hexane solution by the laser flash photolysis technique (LFP). The experimental findings were interpreted using the results of previous matrix isolation studies (Pritchina, E.A.; Gritsan, N.P.; Bally, T.; Zibarev, A.V. Inorg. Chem. 2009, 48, 4075) and high-level quantum chemical calculations. LFP produces two primary intermediates, one of which is the boat-shaped 8-membered cyclic compound (2) and the other is the 6-membered S3N3 cyclic compound carrying an exocyclic (S)–NS group (3). The primary products 2 and 3 absorb a second photon and undergo transformation to the 6-membered S3N3 cycle carrying an exocyclic (N)–SN group (4), which is very unstable and converts back to intermediate 3. The quantum yield of the primary product formation is close to unity even though the quantum yield of photodegradation of 1 is low (∼0.01). Thus, 1 is a photochromic compound undergoing in solution the thermally reversible photochemical isomerization. The mechanism of the photochromic process was established, and the rate constants of the elementary reactions were measured
Yuri P Tsentalovich - One of the best experts on this subject based on the ideXlab platform.
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Photochemistry of Tetrasulfur Tetranitride: Laser Flash Photolysis and Quantum Chemical Study.
ChemInform, 2012Co-Authors: Elena A. Pritchina, Daria S Terpilovskaya, Yuri P Tsentalovich, Matthew S Platz, Nina P. GritsanAbstract:The photochemistry of S4N4 with a highly symmetric cage structure is studied by laser flash photolysis and B3LYP quantum chemical computations.
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photochemistry of Tetrasulfur tetranitride laser flash photolysis and quantum chemical study
Inorganic Chemistry, 2012Co-Authors: Elena A. Pritchina, Daria S Terpilovskaya, Yuri P Tsentalovich, Matthew S Platz, Nina P. GritsanAbstract:The photochemistry of Tetrasulfur tetranitride (1) was studied in hexane solution by the laser flash photolysis technique (LFP). The experimental findings were interpreted using the results of previous matrix isolation studies (Pritchina, E.A.; Gritsan, N.P.; Bally, T.; Zibarev, A.V. Inorg. Chem.2009, 48, 4075) and high-level quantum chemical calculations. LFP produces two primary intermediates, one of which is the boat-shaped 8-membered cyclic compound (2) and the other is the 6-membered S3N3 cyclic compound carrying an exocyclic (S)–N═S group (3). The primary products 2 and 3 absorb a second photon and undergo transformation to the 6-membered S3N3 cycle carrying an exocyclic (N)–S≡N group (4), which is very unstable and converts back to intermediate 3. The quantum yield of the primary product formation is close to unity even though the quantum yield of photodegradation of 1 is low (∼0.01). Thus, 1 is a photochromic compound undergoing in solution the thermally reversible photochemical isomerization. The...
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Photochemistry of Tetrasulfur Tetranitride: Laser Flash Photolysis and Quantum Chemical Study
Inorganic chemistry, 2012Co-Authors: Elena A. Pritchina, Daria S Terpilovskaya, Yuri P Tsentalovich, Matthew S Platz, Nina P. GritsanAbstract:The photochemistry of Tetrasulfur tetranitride (1) was studied in hexane solution by the laser flash photolysis technique (LFP). The experimental findings were interpreted using the results of previous matrix isolation studies (Pritchina, E.A.; Gritsan, N.P.; Bally, T.; Zibarev, A.V. Inorg. Chem. 2009, 48, 4075) and high-level quantum chemical calculations. LFP produces two primary intermediates, one of which is the boat-shaped 8-membered cyclic compound (2) and the other is the 6-membered S(3)N(3) cyclic compound carrying an exocyclic (S)-N═S group (3). The primary products 2 and 3 absorb a second photon and undergo transformation to the 6-membered S(3)N(3) cycle carrying an exocyclic (N)-S≡N group (4), which is very unstable and converts back to intermediate 3. The quantum yield of the primary product formation is close to unity even though the quantum yield of photodegradation of 1 is low (~0.01). Thus, 1 is a photochromic compound undergoing in solution the thermally reversible photochemical isomerization. The mechanism of the photochromic process was established, and the rate constants of the elementary reactions were measured.
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Photochemistry of Tetrasulfur Tetranitride: Laser Flash Photolysis and Quantum Chemical Study
2012Co-Authors: Elena A. Pritchina, Daria S Terpilovskaya, Yuri P Tsentalovich, Matthew S Platz, Nina P. GritsanAbstract:The photochemistry of Tetrasulfur tetranitride (1) was studied in hexane solution by the laser flash photolysis technique (LFP). The experimental findings were interpreted using the results of previous matrix isolation studies (Pritchina, E.A.; Gritsan, N.P.; Bally, T.; Zibarev, A.V. Inorg. Chem. 2009, 48, 4075) and high-level quantum chemical calculations. LFP produces two primary intermediates, one of which is the boat-shaped 8-membered cyclic compound (2) and the other is the 6-membered S3N3 cyclic compound carrying an exocyclic (S)–NS group (3). The primary products 2 and 3 absorb a second photon and undergo transformation to the 6-membered S3N3 cycle carrying an exocyclic (N)–SN group (4), which is very unstable and converts back to intermediate 3. The quantum yield of the primary product formation is close to unity even though the quantum yield of photodegradation of 1 is low (∼0.01). Thus, 1 is a photochromic compound undergoing in solution the thermally reversible photochemical isomerization. The mechanism of the photochromic process was established, and the rate constants of the elementary reactions were measured