Photochemistry of Tetrasulfur Tetranitride: Laser Flash Photolysis and Quantum Chemical Study

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• 作者：Elena A. Pritchina ; Daria S. Terpilovskaya ; Yuri P. Tsentalovich ; Matthew S. Platz ; Nina P. Gritsan
• 刊名：Inorganic Chemistry
• 出版年：2012
• 出版时间：April 16, 2012
• 年：2012
• 卷：51
• 期：8
• 页码：4747-4755
• 全文大小：503K
• 年卷期：v.51,no.8(April 16, 2012)
• ISSN：1520-510X

文摘

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)鈥揘鈺怱 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)鈥揝鈮 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.