Magnetic moment and Mössbauer spectral studies of spin-crossover in tris(N,N'-dialkyldithiocarbamato)iron(III) complexes and their thermal decomposition
Room temperature Mössbauer spectra of tris(N,N'-dialkyldithiocarbamato)iron(III) complexes [(R^sub 2^NCS^sub 2^)^sub 3^Fe] (R = Me, Et, n-Pr, i-Pr, n-Bu and i-Bu) exhibit an asymmetric doublet which can be resolved into two doublets, each corresponding to high and low spin states in equilibrium...
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| Veröffentlicht in: | Transition metal chemistry (Weinheim) 2001-02, Vol.26 (1-2), p.81 |
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| creator | Singhal, Sonal Sharma, Chokhe L Garg, Amar N Chandra, Kailash |
| description | Room temperature Mössbauer spectra of tris(N,N'-dialkyldithiocarbamato)iron(III) complexes [(R^sub 2^NCS^sub 2^)^sub 3^Fe] (R = Me, Et, n-Pr, i-Pr, n-Bu and i-Bu) exhibit an asymmetric doublet which can be resolved into two doublets, each corresponding to high and low spin states in equilibrium. The quadrupole splitting (ΔE^sub Q^), in general, increases with the molecular weight of the alkyl group in both the cases. Plots of magnetic moment (μ^sub eff^) versus temperature show that dimethyl-, diethyl-, di-n-propyl- and di-n-butyl-substituted dithiocarbamato complexes are equilibrium mixtures of high and low spin states at room temperature, but increasingly adopt low spin at the liquid nitrogen temperature. However, the di-i-propyl- and di-i-butyl-substituted dithiocarbamato complexes exhibit primarily low spin state in the 77-350 K range, with a small contribution ( |
| doi_str_mv | 10.1023/A:1007115823823 |
| format | Article |
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The quadrupole splitting (ΔE^sub Q^), in general, increases with the molecular weight of the alkyl group in both the cases. Plots of magnetic moment (μ^sub eff^) versus temperature show that dimethyl-, diethyl-, di-n-propyl- and di-n-butyl-substituted dithiocarbamato complexes are equilibrium mixtures of high and low spin states at room temperature, but increasingly adopt low spin at the liquid nitrogen temperature. However, the di-i-propyl- and di-i-butyl-substituted dithiocarbamato complexes exhibit primarily low spin state in the 77-350 K range, with a small contribution (<15%) of high spin state. Fe--S stretching vibrations in far i.r. region also show spin equilibrium states. Thermogravimetric studies show fast decomposition in the 200-300 °C range, yielding Fe(SCN)^sub 3^ as an intermediate product followed by slow decomposition, leading finally to constant weight corresponding to Fe^sub 2^O^sub 3^ at ca. 650 °C. Mössbauer spectra of the final products of all the complexes exhibit a six line spectrum with H^sub eff^ = 517 ± 3 kOe corresponding to that of α-Fe^sub 2^O^sub 3^ without any possibility of Fe^sub 2^S^sub 3^ as proposed in literature.[PUBLICATION ABSTRACT]</description><identifier>ISSN: 0340-4285</identifier><identifier>EISSN: 1572-901X</identifier><identifier>DOI: 10.1023/A:1007115823823</identifier><language>eng</language><publisher>Dordrecht: Springer Nature B.V</publisher><subject>Molecular weight</subject><ispartof>Transition metal chemistry (Weinheim), 2001-02, Vol.26 (1-2), p.81</ispartof><rights>Kluwer Academic Publishers 2001</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c226t-27bf2ebafb2d08ca1dc230336e3d26ae6bd0c5cba91f9298d01febecce21ca623</citedby></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,27924,27925</link.rule.ids></links><search><creatorcontrib>Singhal, Sonal</creatorcontrib><creatorcontrib>Sharma, Chokhe L</creatorcontrib><creatorcontrib>Garg, Amar N</creatorcontrib><creatorcontrib>Chandra, Kailash</creatorcontrib><title>Magnetic moment and Mössbauer spectral studies of spin-crossover in tris(N,N'-dialkyldithiocarbamato)iron(III) complexes and their thermal decomposition</title><title>Transition metal chemistry (Weinheim)</title><description>Room temperature Mössbauer spectra of tris(N,N'-dialkyldithiocarbamato)iron(III) complexes [(R^sub 2^NCS^sub 2^)^sub 3^Fe] (R = Me, Et, n-Pr, i-Pr, n-Bu and i-Bu) exhibit an asymmetric doublet which can be resolved into two doublets, each corresponding to high and low spin states in equilibrium. The quadrupole splitting (ΔE^sub Q^), in general, increases with the molecular weight of the alkyl group in both the cases. Plots of magnetic moment (μ^sub eff^) versus temperature show that dimethyl-, diethyl-, di-n-propyl- and di-n-butyl-substituted dithiocarbamato complexes are equilibrium mixtures of high and low spin states at room temperature, but increasingly adopt low spin at the liquid nitrogen temperature. However, the di-i-propyl- and di-i-butyl-substituted dithiocarbamato complexes exhibit primarily low spin state in the 77-350 K range, with a small contribution (<15%) of high spin state. Fe--S stretching vibrations in far i.r. region also show spin equilibrium states. Thermogravimetric studies show fast decomposition in the 200-300 °C range, yielding Fe(SCN)^sub 3^ as an intermediate product followed by slow decomposition, leading finally to constant weight corresponding to Fe^sub 2^O^sub 3^ at ca. 650 °C. Mössbauer spectra of the final products of all the complexes exhibit a six line spectrum with H^sub eff^ = 517 ± 3 kOe corresponding to that of α-Fe^sub 2^O^sub 3^ without any possibility of Fe^sub 2^S^sub 3^ as proposed in literature.[PUBLICATION ABSTRACT]</description><subject>Molecular weight</subject><issn>0340-4285</issn><issn>1572-901X</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2001</creationdate><recordtype>article</recordtype><recordid>eNotjctKAzEUhoMoWKtrt8GNLTianMyt7krxMtDWjYK7ktvY1JmkJhnRR_FFfAFfzCkKh3Pg_w_fh9ApJZeUALuaXlNCCkqzElg_e2hAswKSCaHP-2hAWEqSFMrsEB2FsCGEZFCkA_S14C9WRyNx61ptI-ZW4cXPdwiCd9rjsNUyet7gEDtldMCu7jNjE-ldCO69fzEWR2_CaHmxPE-U4c3rZ6NMXBsnuRe85dGNjXd2VFXVGEvXbhv90ZN2prjWxu-2b3uH0rvWBRONs8fooOZN0Cf_d4iebm8eZ_fJ_OGumk3niQTIYwKFqEELXgtQpJScKgmMMJZrpiDnOheKyEwKPqH1BCalIrTWQkupgUqeAxuisz_u1ru3Toe42rjO2165KsuUQF4WwH4BZetujQ</recordid><startdate>20010201</startdate><enddate>20010201</enddate><creator>Singhal, Sonal</creator><creator>Sharma, Chokhe L</creator><creator>Garg, Amar N</creator><creator>Chandra, Kailash</creator><general>Springer Nature B.V</general><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope></search><sort><creationdate>20010201</creationdate><title>Magnetic moment and Mössbauer spectral studies of spin-crossover in tris(N,N'-dialkyldithiocarbamato)iron(III) complexes and their thermal decomposition</title><author>Singhal, Sonal ; Sharma, Chokhe L ; Garg, Amar N ; Chandra, Kailash</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c226t-27bf2ebafb2d08ca1dc230336e3d26ae6bd0c5cba91f9298d01febecce21ca623</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2001</creationdate><topic>Molecular weight</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Singhal, Sonal</creatorcontrib><creatorcontrib>Sharma, Chokhe L</creatorcontrib><creatorcontrib>Garg, Amar N</creatorcontrib><creatorcontrib>Chandra, Kailash</creatorcontrib><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><jtitle>Transition metal chemistry (Weinheim)</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Singhal, Sonal</au><au>Sharma, Chokhe L</au><au>Garg, Amar N</au><au>Chandra, Kailash</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Magnetic moment and Mössbauer spectral studies of spin-crossover in tris(N,N'-dialkyldithiocarbamato)iron(III) complexes and their thermal decomposition</atitle><jtitle>Transition metal chemistry (Weinheim)</jtitle><date>2001-02-01</date><risdate>2001</risdate><volume>26</volume><issue>1-2</issue><spage>81</spage><pages>81-</pages><issn>0340-4285</issn><eissn>1572-901X</eissn><abstract>Room temperature Mössbauer spectra of tris(N,N'-dialkyldithiocarbamato)iron(III) complexes [(R^sub 2^NCS^sub 2^)^sub 3^Fe] (R = Me, Et, n-Pr, i-Pr, n-Bu and i-Bu) exhibit an asymmetric doublet which can be resolved into two doublets, each corresponding to high and low spin states in equilibrium. The quadrupole splitting (ΔE^sub Q^), in general, increases with the molecular weight of the alkyl group in both the cases. Plots of magnetic moment (μ^sub eff^) versus temperature show that dimethyl-, diethyl-, di-n-propyl- and di-n-butyl-substituted dithiocarbamato complexes are equilibrium mixtures of high and low spin states at room temperature, but increasingly adopt low spin at the liquid nitrogen temperature. However, the di-i-propyl- and di-i-butyl-substituted dithiocarbamato complexes exhibit primarily low spin state in the 77-350 K range, with a small contribution (<15%) of high spin state. Fe--S stretching vibrations in far i.r. region also show spin equilibrium states. Thermogravimetric studies show fast decomposition in the 200-300 °C range, yielding Fe(SCN)^sub 3^ as an intermediate product followed by slow decomposition, leading finally to constant weight corresponding to Fe^sub 2^O^sub 3^ at ca. 650 °C. Mössbauer spectra of the final products of all the complexes exhibit a six line spectrum with H^sub eff^ = 517 ± 3 kOe corresponding to that of α-Fe^sub 2^O^sub 3^ without any possibility of Fe^sub 2^S^sub 3^ as proposed in literature.[PUBLICATION ABSTRACT]</abstract><cop>Dordrecht</cop><pub>Springer Nature B.V</pub><doi>10.1023/A:1007115823823</doi></addata></record> |
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| subjects | Molecular weight |
| title | Magnetic moment and Mössbauer spectral studies of spin-crossover in tris(N,N'-dialkyldithiocarbamato)iron(III) complexes and their thermal decomposition |
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